Ambiphilic Hydrogen in Trisubstituted Silanes: Substituent- Driven Polarity Flip Confirmed by NMR

Ambiphilic Hydrogen in Trisubstituted Silanes: Substituent- Driven Polarity Flip Confirmed by NMR | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Ambiphilic Hydrogen in Trisubstituted Silanes: Substituent- Driven Polarity Flip Confirmed by NMR Pavel Hobza, Rabindranath Lo, Debashree Manna, Vítězslav Hrubý This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7574907/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 20 Mar, 2026 Read the published version in Communications Chemistry → Version 1 posted You are reading this latest preprint version Abstract Atomic partial charges are local, model-dependent descriptors that often fail to capture the global electrostatic environment governing noncovalent interactions and reactivity. Here we show that the molecular electrostatic potential (ESP) at the Si–H hydrogen in trisubstituted silanes is a decisive predictor of electrophilic versus nucleophilic behavior, whereas local charges alone are misleading. Using PBE0-D3/def2-TZVPP calculations, we evaluated atomic charges and ESP extrema in the gas phase and in two solvents, benzene and o-dichlorobenzene. Electron-donating groups (EDGs) generate hydridic hydrogens with a negative ESP near H (nucleophilic), while electron-withdrawing groups (EWGs) generally retain a negative local charge on H but induce a positive ESP region along the Si–H axis (electrophilic). These effects are solvent dependent: with increasing dielectric constant, V s,max at H becomes more negative for EDG-substituted silanes and more positive for EWG-substituted silanes. The same solvent influence is mirrored in ¹H NMR chemical shifts, producing upfield shifts for EDG- and downfield shifts for EWG-substituted silanes. Targeted experimental NMR measurements validate these predictions. The positive ESP region near H in EWG-substituted silanes is σ-hole-like in directionality, but unlike classical σ-holes arising from lone-pair depletion (e.g., halogens, chalcogens), it reflects a collective molecular ESP effect. Physical sciences/Chemistry/Theoretical chemistry/Computational chemistry Physical sciences/Chemistry/Analytical chemistry/NMR spectroscopy/Solution-state NMR Figures Figure 1 Figure 2 Figure 3 Introduction The distribution of electron density around a molecule plays a crucial role in determining its chemical reactivity and intermolecular interactions. 1 , 2 Traditionally, this distribution is analyzed by calculating atomic charges using various theoretical models. 3 , 4 However, atomic charges are only local properties and are not easily observable quantities. In contrast, the molecular electrostatic potential (ESP), which takes into account both the nuclear charges and the electron densities of all atoms in a molecule, is a global, easily observable property that provides a more comprehensive and physically meaningful description. 5 – 12 A comprehensive understanding of a molecule’s reactivity and its propensity for noncovalent interactions requires considering both atomic partial charges and the overall topology of the ESP. Generally, the regions of maximum and minimum ESP ( V ₛ,max and V ₛ,min ) coincide with the most positive and negative atomic charges, respectively. Notable exceptions exist, however, where atomic charges fail to capture the true ESP distribution. In such cases, it is the ESP, not the atomic charges, that determines whether a molecule behaves as an electrophile or a nucleophile. One of the clearest examples of this mismatch is the anisotropic electron density around a halogen covalently bonded to carbon (R–X), which creates a positive ESP region (the σ-hole) opposite the R–X bond. 13 This concept was extensively developed by Peter Politzer, Jane S. Murray, and Timothy Clark, who advocated the umbrella term “σ-hole bonding” for interactions involving such regions, encompassing halogen, chalcogen, pnictogen, tetrel, and triel bonds. 14 – 16 The σ-hole concept was introduced to rationalize the counterintuitive electrophilicity of halogens covalently bound to carbon. Despite their higher electronegativity and the resulting net negative atomic charge, these halogens often act as electrophiles. A positive σ-hole resolves the paradox, a localized maximum in the ESP along the extension of the R–X bond, which engages attractively with electron-rich sites. This behavior highlights the limitations of atom-centered charges and underscores the importance of ESP in accurately describing reactivity and noncovalent interactions. 10 The situation for chemical bonds involving the lightest element, hydrogen, is notably different. In bonds such as F-H, O-H, N-H, and also C-H, the heavier atom (Y) is generally more electronegative than hydrogen. Consequently, the Y-H bond is polarized towards the heavier atom (Y), rendering the hydrogen atom partially positive, or protic. This protic nature of hydrogen remains generally consistent regardless of the substituents attached to the heavy atom or the broader molecular environment. By contrast, for the heavier Group 14 elements, i.e., silicon, germanium, and tin, the trend reverses. Since these atoms are more electropositive than hydrogen (Pauling electronegativities: Si 1.74, Ge 2.02, Sn 1.72 vs H 2.20), Y–H bonds are polarized toward hydrogen, giving H a negative partial charge, making them hydridic in nature. Such hydridic hydrogen forms non-covalent complexes with various types of electron acceptors, including positive σ-, π-, and p-holes confirmed by theoretical and experimental studies. 17 , 18 Furthermore, silanes act as a versatile hydride source for catalytic reactions. 19 Crucially, however, a negative atomic charge on hydrogen does not necessarily imply a negative ESP in its vicinity. Substituents on the tetrel center might markedly reshape the local ESP at H, and even invert its sign. In unsubstituted silane (SiH₄), hydrogen is hydridic (q = − 0.141), yet the corresponding V ₛ, max in the vicinity of H is slightly positive (+ 1.73). 20 In substituted silanes, the hydrogen typically retains a negative partial charge, but the ESP near H can change dramatically with the nature of the substituents. Consequently, the region around H may be either ESP-positive or ESP-negative, enabling the silane hydrogen to behave as an electrophile or a nucleophile under different conditions. For completeness, we also examined other hydrogen-containing bonds that could exhibit related behavior. In Al–H bonds, the strong electropositivity of aluminum renders hydrogen hydridic, and the ESP near H can switch sign with substitution, closely paralleling the Si–H case. By contrast, C–H and P–H bonds remain consistently protic with positive ESP near hydrogen, regardless of the substitutions considered. Thus, within the neutral molecules, silicon represents a rare nonmetal capable of displaying ambiphilic behavior at the Y–H bond. This study investigates the electronic structure and ambiphilic behavior of Si-H in trisubstituted silanes in the gas phase and in two solvents, benzene (BEN) and o-dichlorobenzene (o-DCB), with computational results complemented and validated by experimental NMR spectroscopy. Results and Discussion The structures and charge distributions of trisubstituted silanes were investigated by DFT at the PBE0-D3/def2-TZVPP level. Calculations were performed in the gas phase and in BEN and o-DCB using a polarizable continuum model (dielectric constants 2.27 and 9.99 for BEN and o-DCB, respectively). Substituents spanned electron-withdrawing groups (EWGs: F, Cl, Br, CF₃, CN, NO₂, C 6 F 5 ) to electron-donating groups (EDGs: Me, Et, i Pr, Ph, NH₂, NMe₂). For each silane, we determined atomic charges and the extrema of the electrostatic potential on the molecular surface ( V ₛ, max, V ₛ, min ; Table 1 , Fig. 1 ). Optimized structures are shown in Figure S1 . We first discuss hydrogen atomic charges computed using NBO (Natural Bond Orbital), Mulliken, Hirshfeld, ADCH (atomic dipole moment corrected Hirshfeld) and CM5 (Charge Model 5) schemes (Table 1 ). NBO yields the largest magnitudes, whereas Mulliken and Hirshfeld give smaller and mutually similar values. In BEN and o-DCB, hydrogen charges become less negative for EWG-substituted silanes and more negative for EDG-substituted silanes. Notably, for EWG-substituted systems, the hydrogen charges calculated from NBO, 21 Mulliken, Hirshfeld 22 at hydridic H do not correlate with the ESP, whereas for EDG-substituted silanes, they correlate well. However, the partial charges derived from the ADCH 23 and CM5 24 methods exhibit a comparatively stronger correlation with the ESP in EWG-substituted systems. 25 Both methods employ Hirshfeld population analysis, which partitions the molecular electron density to determine partial atomic charges. A central result is the mismatch that can arise between local atomic charge and the global electrostatic potential (ESP) at hydrogen. For EDG-substituted silanes, however, the picture is straightforward: all charge schemes (NBO, Mulliken, Hirshfeld, ADCH, CM5) assign a negative partial charge to H, and the surface ESP at H is likewise negative. Accordingly, H behaves as a nucleophilic, hydridic site. The ESP around H is anisotropic: it is least negative at the axial “pole” along the Si–H bond and most negative around the equatorial “belt” (Table 1 ), where V ₛ,min is located (see later). For EWG-substituted silanes, an intriguing inversion appears. Most of the charge-partitioning schemes still assign H a negative partial charge, seemingly indicating a nucleophilic site, but the surface ESP near H tells a different story: V ₛ, max along the Si–H axis is positive, marking H as electrophilic. Strong electron withdrawal by the substituents, together with the resulting positive polarization of the silicon center, depletes electron density in the Si–H bond direction and creates a σ-hole–like positive lobe at H. The local charge on H remains negative because, within the Si–H bond, H still integrates to slightly more electron density than a neutral atom. Nonetheless, the global electrostatic environment is dominated by the surrounding framework, so these hydrogens behave as electrophiles in their interactions. The data make this clear: in EWG-substituted silanes, V ₛ, max at H is positive, signaling an electron-poor region, even though the atomic charge on H is negative. Crucially, it is the sign of the ESP at H, not q(H), that tracks reactivity. A negative ESP at H (typical for EDG-substituted silanes) corresponds to a nucleophilic, hydridic hydrogen capable of donating electron density. A positive ESP at H (typical for EWG-substituted silanes) marks an electrophilic, electron-deficient hydrogen, akin to a protic site. Relying on local charges alone would incorrectly label all these silanes as bearing nucleophilic (hydridic) hydrogens; the ESP analysis instead reveals a sharp division, EDG-silanes maintain nucleophilic H, whereas EWG-silanes flip to electrophilic H. A natural question is whether the ambiphilic behavior observed for Si–H, in which substitution toggles the hydrogen between nucleophilic and electrophilic character, also occurs for other Y–H bonds, particularly those with small electronegativity differences between Y and H. Tables S1-S6 compile partial atomic charges and ESP values (PBE0-D3/def2-TZVPP) for X₃C–H, X₃Ge–H, X₃Sn–H, X₃Pb–H, X₂Al–H, and X₂P–H with both EWG and EDG substituents. Only carbon is more electronegative than hydrogen; all other elements considered are more electropositive. Using Δχ ≡ χ(H) − χ(X), the differences are − 0.30 (C), + 0.46 (Si), + 0.18 (Ge), + 0.48 (Sn), + 0.64 (Pb), + 0.73 (Al), and + 0.14 (P). For X₃C–H, hydrogen is protic for all substituents considered and the ESP at H is positive, consistent with electrophilic behavior. X₂P–H systems likewise show systematically positive ESP at H and are electrophilic. Upon moving to solvent (BEN, o-DCB), both q(H) and V ₛ, max shift to more positive values in these two families. X₂Al–H behaves differently. Here, H is uniformly hydridic, yet ESP at H depends on substitution: it is positive for EWG-substituted alanes and negative for EDG-substituted alanes, mirroring the X₃Si–H case. Accordingly, EDG-substituted alanes feature nucleophilic H, whereas EWG-substituted alanes display electrophilic H. Increasing solvent polarity drives ESP at H more negative for EDG cases and more positive for EWG cases. Solvent effects were not considered in all remaining molecules, and only the gas phase calculations were performed. Table 1 The calculated Mulliken, Natural Bond Orbital, Hirshfeld, ADCH and CM5 charges (in e) on the H and Si atoms of X 3 Si-H in various medium at the PBE0-D3/def2-TZVPP level of theory. The extrema of the ESP on the molecular surface in the vicinity of H atom given in kcal/mol. X 3 Si-H Mulliken NBO Hirshfeld ADCH CM5 ESP H Si H Si H Si H Si H Si SiH 4 Gas -0.047 0.187 -0.141 0.562 -0.067 0.267 -0.030 0.118 0.013 -0.052 1.73 BEN -0.047 0.190 -0.141 0.563 -0.067 0.267 -0.030 0.119 0.013 -0.052 1.71 o-DCB -0.048 0.192 -0.141 0.564 -0.067 0.267 -0.030 0.119 0.013 -0.052 1.70 F 3 SiH Gas -0.070 0.915 -0.277 2.185 -0.043 0.595 -0.013 0.541 0.045 0.438 16.10 BEN -0.056 0.932 -0.263 2.183 -0.034 0.601 0.005 0.557 0.055 0.443 19.17 o-DCB -0.045 0.943 -0.251 2.180 -0.027 0.605 0.019 0.568 0.062 0.447 21.62 Cl 3 SiH Gas -0.039 0.603 -0.165 1.183 -0.048 0.350 0.013 0.190 0.038 0.131 12.88 BEN -0.027 0.615 -0.155 1.186 -0.041 0.356 0.026 0.199 0.046 0.137 15.44 o-DCB -0.018 0.623 -0.146 1.188 -0.035 0.360 0.037 0.206 0.052 0.142 17.55 Br 3 SiH Gas -0.018 0.485 -0.148 0.882 -0.047 0.280 0.023 0.106 0.038 0.010 12.92 BEN -0.007 0.499 -0.139 0.886 -0.040 0.285 0.036 0.112 0.045 0.016 15.33 o-DCB 0.001 0.509 -0.131 0.889 -0.034 0.289 0.046 0.117 0.051 0.021 17.37 (C 6 F 5 ) 3 SiH Gas -0.013 0.353 -0.121 1.335 -0.059 0.323 -0.030 0.434 0.029 0.111 7.18 BEN -0.016 0.344 -0.121 1.337 -0.059 0.327 -0.029 0.511 0.029 0.115 7.90 o-DCB -0.018 0.339 -0.121 1.338 -0.059 0.329 -0.029 0.573 0.030 0.118 8.57 (CF 3 ) 3 SiH Gas -0.007 0.175 -0.123 0.939 -0.033 0.325 0.032 0.178 0.053 0.138 22.82 BEN 0.008 0.183 -0.108 0.943 -0.022 0.335 0.049 0.193 0.064 0.148 27.04 o-DCB 0.020 0.189 -0.096 0.947 -0.014 0.343 0.065 0.205 0.072 0.156 30.52 (CN) 3 SiH Gas -0.005 0.538 -0.093 1.169 -0.018 0.482 0.042 0.393 0.068 0.286 31.77 BEN 0.011 0.568 -0.073 1.174 -0.004 0.505 0.065 0.501 0.082 0.309 38.55 o-DCB 0.025 0.589 -0.056 1.177 0.008 0.523 0.085 0.613 0.095 0.328 44.30 (NO 2 ) 3 SiH Gas 0.026 0.521 -0.112 1.430 -0.006 0.447 0.052 0.128 0.093 0.452 34.40 BEN 0.044 0.548 -0.093 1.437 0.010 0.473 0.074 0.054 0.108 0.477 41.41 o-DCB 0.060 0.571 -0.076 1.442 0.023 0.494 0.095 -0.126 0.120 0.498 47.75 Ph 3 SiH Gas -0.082 0.327 -0.173 1.384 -0.080 0.308 -0.054 0.597 0.002 0.090 -5.34 a /-7.02 BEN -0.086 0.346 -0.175 1.387 -0.081 0.308 -0.057 0.805 0.000 0.090 -6.28 a /-8.12 o-DCB -0.088 0.357 -0.177 1.389 -0.082 0.307 -0.057 0.966 0.000 0.089 -6.68 (iPr) 3 SiH Gas -0.076 0.201 -0.196 1.428 -0.089 0.306 -0.077 0.216 -0.009 0.065 -8.25 BEN -0.092 0.203 -0.205 1.433 -0.095 0.306 -0.087 0.218 -0.015 0.065 -9.86 o-DCB -0.105 0.204 -0.212 1.438 -0.100 0.306 -0.096 0.219 -0.020 0.064 -11.31 Me 3 SiH Gas -0.100 0.382 -0.197 1.371 -0.092 0.325 -0.075 0.250 -0.012 0.080 -8.13 a /-8.65 BEN -0.115 0.395 -0.207 1.378 -0.098 0.325 -0.087 0.255 -0.018 0.079 -9.90 a /-10.21 o-DCB -0.127 0.403 -0.215 1.384 -0.103 0.324 -0.097 0.259 -0.024 0.079 -11.36 a /-11.53 Et 3 SiH Gas -0.092 0.328 -0.198 1.385 -0.091 0.312 -0.078 0.222 -0.011 0.068 -8.27 a /-8.60 BEN -0.107 0.334 -0.208 1.391 -0.097 0.312 -0.089 0.225 -0.017 0.067 -10.09 a /-10.25 o-DCB -0.119 0.338 -0.216 1.395 -0.102 0.312 -0.099 0.227 -0.023 0.067 -11.62 a /-11.69 (Me 3 Si) 3 SiH Gas -0.081 -0.043 -0.093 -0.204 -0.077 0.021 -0.028 -0.091 0.004 -0.069 -6.10 a /-7.54 BEN -0.062 -0.089 -0.102 -0.205 -0.083 0.018 -0.039 -0.093 -0.003 -0.072 -8.00 a /-9.18 o-DCB -0.099 -0.075 -0.109 -0.206 -0.088 0.016 -0.049 -0.093 -0.008 -0.074 -9.80 a /-10.77 (NH 2 ) 3 SiH Gas -0.129 0.542 -0.255 1.810 -0.099 0.348 -0.082 0.420 -0.009 0.337 -13.14 BEN -0.140 0.550 -0.263 1.809 -0.104 0.342 -0.092 0.444 -0.015 0.330 -14.86 o-DCB -0.173 0.588 -0.282 1.825 -0.117 0.341 -0.096 0.482 -0.030 0.328 -13.75 (Me 2 N) 3 SiH Gas -0.113 0.262 -0.252 1.899 -0.093 0.357 -0.076 0.292 -0.003 0.347 -10.50 BEN -0.122 0.270 -0.259 1.902 -0.099 0.352 -0.086 0.297 -0.009 0.342 -12.57 o-DCB -0.129 0.273 -0.265 1.905 -0.103 0.347 -0.094 0.300 -0.014 0.338 -14.66 a The V s,min of H atom on the extension of Si-H. Table 2 The proton chemical shifts of silanes, as well as their corresponding differences in two solvents, calculated at the PBE0-D3/def2-TZVPP level of theory using the COSMO continuum solvation model in benzene and o-DCB. The experimental proton chemical shifts of the silanes are also provided. Silane Medium Calculated 1 H chemical shifts a Experimental 1 H chemical shifts 1 H δ ppm Relative Δδ 1 H ppm 1 H δ ppm Relative Δδ 1 H ppm (C 6 F 5 ) 3 Si-H BEN 6.609 0.002 5.81 0.14 o-DCB 6.611 5.95 (Me 3 Si) 3 Si-H BEN 2.635 -0.121 2.54 -0.23 o-DCB 2.514 2.31 Et 3 SiH BEN 4.017 -0.089 3.90 -0.21 o-DCB 3.928 3.69 Ph 3 SiH BEN 6.203 -0.037 5.71 -0.21 o-DCB 6.166 5.50 a 1H NMR of TMS taken as a reference with the isotropic shielding value of 31.506 ppm . These results highlight the superiority of a global, ESP-based description over purely local charge analyses for understanding and predicting reactivity. In particular, ESP mapping accurately distinguishes silanes that act as hydride donors from those exhibiting protic, electrophilic behavior, a distinction that partial atomic charges alone fail to capture. While local charge analysis would suggest uniformly nucleophilic behavior for all silanes, a global ESP-based approach correctly predicts electrophilic behavior for EWG-substituted silanes and nucleophilic behavior for EDG-substituted silanes. To validate this, we examined silanes in two aprotic solvents, BEN and o-DCB. Upon moving from the gas phase to solvent, V ₛ,max at H shifts more positive for EWG-substituted silanes and more negative for EDG-substituted silanes. To support these theoretical trends, we recorded ¹H NMR spectra for four commercially available silanes, ((C₆F₅)₃Si–H, (Me₃Si)₃Si–H, Et₃SiH, and Ph₃SiH) in BEN and o-DCB. As shown in Table 1 , (C₆F₅)₃Si–H exhibits a positive ESP at H, whereas the others show a negative ESP at H. The experimental chemical shifts are summarized in Tables 2 and S7 and compared with values computed at the PBE0-D3/def2-TZVPP 26–28 level using the COSMO 29 continuum model. Experimental details and individual spectra are provided in the Supporting Information (Figures S2–S9). Protic hydrogens typically exhibit modest, polarity-dependent solvent shifts and tend to move downfield as solvent polarity increases. 30 , 31 We observe this behavior for the EWG-substituted silane (C₆F₅)₃Si–H: V ₛ,max at H becomes more positive upon going from BEN to o-DCB, and a downfield shift of the ¹H resonance (Table 2 , Fig. 2 ). In contrast, EDG-substituted silanes ((Me₃Si)₃Si–H, Et₃SiH, and Ph₃SiH) show the opposite trend (Table 2 , Fig. 2 ), in line with their negative V ₛ,max values: increasing solvent polarity drives V ₛ,max more negative and shifts the ¹H signal upfield. In NMR, the observed chemical shift (δ) depends on how much the local electrons oppose the external magnetic field (B₀). A more negative ESP at H means the region around H is richer in electron density (from bond polarization and substituent effects). This increased local electron density can partially shield the nucleus from B₀. When electron density circulates under B₀, it generates an induced magnetic field (B ind ) that opposes B₀ at the nucleus. Thus, higher electron density reduces the effective magnetic field at the nucleus (B eff = B₀ – B ind ). This means the nucleus resonates at a higher field strength (upfield) and shows a lower δ value (shielding). In contrast, a positive ESP at H means electron density is drawn away, leaving H electron-poor. With fewer shielding electrons, the nucleus feels more of B₀. This results in deshielding or downfield shift (larger δ) of H. Atomic charges are intrinsically local properties, whereas both the ESP and NMR chemical shifts capture not only local electron density but also the broader molecular environment and intermolecular influences. Thus, ESP and NMR chemical shifts show consistent trends and reinforce each other, in line with the expectation. Since both BEN and o-DCB are aromatic, differential ring-current effects are minimized, so the observed chemical-shift changes can be attributed primarily to solvent polarity. ¹H NMR measurements in BEN and o-DCB corroborate the divergent reactivity of EWG- and EDG-substituted silanes, supporting the ESP-based, non-local description of charge distribution. A comprehensive computational analysis was performed for Et₃SiH and trichlorosilane in the gas phase and in four additional solvents: chloroform, acetone, acetonitrile, and DMSO. Because these calculations used the implicit COSMO model, solvent effects are governed solely by the dielectric constant (ε); features such as protic/aprotic character and aromaticity are not represented. For EWG- versus EDG-substituted silanes, the influence of solvent polarity on ¹H chemical shifts, V ₛ,max values, and dipole moments follows opposite trends (Fig. 3 ). In the EDG-substituted silane Et₃SiH, increasing ε decreases both V ₛ,max , and the dipole moment, accompanied by an upfield shift of the Si–H ¹H resonance. In contrast, in the EWG-substituted trichlorosilane, increasing ε raises Vₛ , max , and the dipole moment and produces a downfield shift of the Si–H ¹H signal. These opposing behaviors reflect the positive ESP induced by EWGs. Because the dipole vectors of EWG- and EDG-substituted silanes are oriented in opposite directions, we plot dipole moments for the EDG cases with a negative sign for consistency. As shown in Fig. 3 , solvent effects are most pronounced at low ε and become negligible at higher ε. We have shown that in EWG-substituted silanes the V ₛ,max near H becomes positive. This resembles the positive σ-hole observed for halogens covalently bonded to carbon. Figure 1 illustrates the parallel by comparing the anisotropic ESP in bromobenzene (Fig. 1 a) and trichlorosilane (Fig. 1 b). In bromobenzene, although Br bears a net negative atomic charge, a pronounced positive region, the σ-hole, appears along the extension of the C–Br bond, while a belt of negative potential lies perpendicular to this axis. Here, within the σ-hole, the ESP is uniformly positive relative to its surroundings. Trichlorosilane shows an analogous anisotropy around the hydridic hydrogen: despite a negative partial charge on H, a positive ESP “cap” is found along the Si–H axis (the pole), and even the equatorial belt remains positive ( ≈ + 11.1) though less than at the pole ( ≈ + 12.9). Consequently, the Si–H bond in such silanes acts exclusively as an electrophilic site. In halogens such as bromine, the σ-hole arises from an anisotropic electron distribution associated with the presence of lone pairs, allowing the atom to act as an electrophile along the bond axis and as a nucleophile in the perpendicular belt. This can be rationalized either as a depletion of electron density along the C–Br extension or, qualitatively, as a change in hybridization (sp³ → sp²) that allocates five valence electrons to two lone pairs and the C–Br σ bond, leaving the third lone pair empty. This region along the bond axis constitutes the σ-hole. Hydrogen, by contrast, has no core shell or lone pairs to redistribute; its ESP anisotropy in substituted silanes stems from the collective molecular electron distribution rather than depletion of a localized pair. In triethylsilane (Fig. 1 c), H carries a negative partial charge and the nearby ESP is negative and nearly uniform; a slight anisotropy remains, with the pole ( ≈ − 8.3) being marginally less negative (i.e., more positive) than the belt ( ≈ − 8.6). For comparison, chloroform (Fig. 1 d) features a protic hydrogen with a positive ESP in its vicinity. Conclusion In summary, the molecular electrostatic potential, not local atomic charges, is the reliable descriptor for predicting and rationalizing the behavior of the Si-H of trisubstituted silanes. Across PBE0-D3/def2-TZVPP computations in the gas phase and in benzene and o-dichlorobenzene, corroborated by solvent-dependent ¹H NMR shifts, we find a clear, substituent-controlled dichotomy: EDG-substituted silanes: Hydrogens are hydridic and nucleophilic: q(H) < 0 and the surface ESP near H is negative. Increasing solvent polarity drives ESP more negative and shifts the Si–H resonance upfield, consistent with an electron-rich H. EWG-substituted silanes: Hydrogens are hydridic yet electrophilic: q(H) < 0 but the surface ESP near H is positive. Higher dielectric media make ESP more positive and shift the Si–H resonance downfield, revealing an electron-poor H. Local charges alone would incorrectly predict uniform nucleophilicity across both series. Thus, ESP provides a robust, transferable predictor of Si–H reactivity. σ-hole analogy: The positive region near H in EWG-substituted silanes is σ-hole-like in directionality but does not arise from lone-pair depletion on hydrogen; it reflects a collective, molecular ESP effect. Generalization to other Y–H bonds with small Y/H electronegativity gaps reveals consistent behavior: X₃C–H and X₂P–H remain protic with positive ESP at H (electrophilic) across all cases studied, whereas X₂Al–H mirrors Si–H by exhibiting an ESP-governed switch. Si–H is unusual among neutral nonmetals for its ability to exhibit pronounced ambiphilic behavior. Thus, global ESP features—particularly V ₛ ,max, V ₛ ,min at H—outperform local partial charges as predictors of electrophilic versus nucleophilic character. These insights provide practical guidelines for engineering noncovalent interactions, tuning Si–H reactivity in synthesis and catalysis, and avoiding misassignments that arise from relying solely on local atomic charges while neglecting the global electrostatic field. Methods Computational details All molecular geometries were optimized using density functional theory (DFT) at the PBE0-D3 26,27 level with the def2-TZVPP basis set. 28 Vibrational frequency calculations were carried out at the same level to verify that the optimized structures correspond to local minima (no imaginary frequencies). Solvent effects of benzene and o-dichlorobenzene were included during geometry optimizations via the COSMO continuum solvation model. 29 All computations were performed using the Gaussian 16 software package. 32 Atomic partial charges were determined using Natural Bond Order (NBO), 21 Hirshfeld, 22 and charge model 5 (CM5) methods 23 within Gaussian 16. Additionally, atomic dipole–corrected Hirshfeld (ADCH) charges 24 and the maximum electrostatic potential ( V s,max ) near hydrogen atoms were calculated using the Multiwfn program. 33 NMR chemical shifts for the optimized geometries were calculated using the Gauge-Including Atomic Orbital (GIAO) method, 34 with tetramethylsilane (TMS) employed as the reference standard. Declarations Competing interests The authors declare no competing interests. Author contributions P.H. supervised the project. R.L. and D. M. carried out the quantum chemical calculations. V. H. performed the experiments. All authors discussed the results and commented on the manuscript. Acknowledgments This article has been produced with the financial support of the European Union under the REFRESH – Research Excellence for Region Sustainability and High-tech Industries project number CZ.10.03.01/00/22_003/0000048 via the Operational Programme Just Transition (P.H.). V.H. acknowledges the support from ERDF/ESF Project TECHSCALE (Grant CZ.02.01.01/00/22_008/0004587). Data Availability Statement The data that support the findings of this study are available in the supporting information of this article. The publication data will be made available at ZENODO after manuscript acceptance. Additional Information Supplementary information The online version contains supplementary material available at References Feynman RP (1939) Forces in Molecules. Phys Rev 56:340–343 Suresh CH, Anila S (2023) Molecular Electrostatic Potential Topology Analysis of Noncovalent Interactions. Acc Chem Res 56:1884–1895 Cho M et al (2020) The Atomic Partial Charges Arboretum: Trying to See the Forest for the Trees. ChemPhysChem 21, 688–696 Mahmoudi S et al (2025) Experimental determination of partial charges with electron diffraction. Nature. 10.1038/s41586-025-09405-0 Murray JS, Politzer P (2011) The electrostatic potential: an overview. WIREs Comput Mol Sci 1:153–163 Bulat FA, Toro-Labbé A, Brinck T, Murray JS, Politzer P (2010) Quantitative analysis of molecular surfaces: areas, volumes, electrostatic potentials and average local ionization energies. J Mol Model 16:1679–1691 Politzer P, Landry SJ, Waernheim T (1982) Proposed procedure for using electrostatic potentials to predict and interpret nucleophilic processes. J Phys Chem 86:4767–4771 Politzer P, Laurence PR, Jayasuriya K (1985) Molecular electrostatic potentials: an effective tool for the elucidation of biochemical phenomena. Environ Health Perspect 61:191–202 Brinck T, Murray JS, Politzer P (1992) Surface electrostatic potentials of halogenated methanes as indicators of directional intermolecular interactions. Int J Quantum Chem 44:57–64 Suresh CH, Remya GS, Anjalikrishna PK (2022) Molecular electrostatic potential analysis: A powerful tool to interpret and predict chemical reactivity. WIREs Comput Mol Sci 12:e1601 Haritha M, Suresh CH (2023) The fundamental nature and importance of electrostatic potential in hydrogen bond formation: a case study of heterocycles frequently observed in drugs. New J Chem 47:17323–17332 Shin D, Jung Y (2022) Molecular electrostatic potential as a general and versatile indicator for electronic substituent effects: statistical analysis and applications. Phys Chem Chem Phys 24:25740–25752 Mallada B et al (2021) Real-space imaging of anisotropic charge of σ-hole by means of Kelvin probe force microscopy. Science 374:863–867 Politzer P, Murray JS, Clark T (2013) Halogen bonding and other σ-hole interactions: a perspective. Phys Chem Chem Phys 15:11178 Clark T, Hennemann M, Murray JS, Politzer P (2007) Halogen bonding: the σ-hole: Proceedings of Modeling interactions in biomolecules II, Prague, September 5th–9th, 2005. J Mol Model 13, 291–296 Kolář MH, Hobza P (2016) Computer Modeling of Halogen Bonds and Other σ-Hole Interactions. Chem Rev 116:5155–5187 Manna D et al (2025) Beyond Deshielding: NMR Evidence of Shielding in Hydridic and Protonic Hydrogen Bonds. J Chem Theory Comput 21:7495–7502 Civiš S et al (2023) Hydrogen Bonding with Hydridic Hydrogen–Experimental Low-Temperature IR and Computational Study: Is a Revised Definition of Hydrogen Bonding Appropriate? J Am Chem Soc 145:8550–8559 Mirza YK, Bera PS, Mohite SB, Pandey AK, Bera M (2024) Silanes as a versatile hydride source for Ni–H catalysis: a promising tool for π-hydro functionalization. Org Chem Front 11:4290–4317 Scheiner S (2025) Lower limits on hydrogen bond strength. Charge of bridging H atom. Phys Chem Chem Phys 27:10283–10290 Reed AE, Curtiss LA, Weinhold F (1988) Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint. Chem Rev 88:899–926 Hirshfeld FL (1977) Bonded-atom fragments for describing molecular charge densities. Theoret Chim Acta 44:129–138 Lu T, Chen F, ATOMIC DIPOLE MOMENT (2012) CORRECTED HIRSHFELD POPULATION METHOD. J Theor Comput Chem 11:163–183 Marenich AV, Jerome SV, Cramer CJ, Truhlar DG (2012) Charge Model 5: An Extension of Hirshfeld Population Analysis for the Accurate Description of Molecular Interactions in Gaseous and Condensed Phases. J Chem Theory Comput 8:527–541 Qin L et al (2024) The strongest dative bond in main-group compounds. Theoretical study of OAeF – (Ae = Be–Ba). Phys Chem Chem Phys 26:24294–24313 Adamo C, Barone V (1999) Toward reliable density functional methods without adjustable parameters: The PBE0 model. J Chem Phys 110:6158–6170 Grimme S, Antony J, Ehrlich S, Krieg H (2010) A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J Chem Phys 132:154104 Weigend F, Ahlrichs R (2005) Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. Phys Chem Chem Phys 7:3297 Klamt A, Schüürmann G (1993) COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient. J Chem Soc Perkin Trans 2:799–805. 10.1039/P29930000799 Fulmer GR et al (2010) NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the Organometallic Chemist. Organometallics 29:2176–2179 Goyary S, Sarmah MJ, Goswami HP, Nath N (2024) Solvent-induced 1H NMR chemical shifts of annulenes. Comput Theor Chem 1236:114601 Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Petersson GA, Nakatsuji H, Li X, Caricato M, Marenich AV, Bloino J, Janesko BG, Gomperts R, Mennucci B, Hratchian HP, Ortiz JV, Izmaylov AF, Sonnenberg JL, Williams-Young D, Ding F, Lipparini F, Egidi F, Goings J, Peng B, Petrone A, Henderson T, Ranasinghe D, Zakrzewski VG, Gao J, Rega N, Zheng G, Liang W, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Throssell K, Montgomery JA Jr., Peralta JE, Ogliaro F, Bearpark MJ, Heyd JJ, Brothers EN, Kudin KN, Staroverov VN, Keith TA, Kobayashi R, Normand J, Raghavachari K, Rendell AP, Burant JC, Iyengar SS, Tomasi J, Cossi M, Millam JM, Klene M, Adamo C, Cammi R J. W. Ochterski, R. L. Martin, K. Morokuma, O. Farkas, J. B. Foresman, and D. J. Fox. Gaussian. Lu T, Chen F, Multiwfn (2012) A multifunctional wavefunction analyzer. J Comput Chem 33:580–592 Wolinski K, Hinton JF, Pulay P (1990) Efficient implementation of the gauge-independent atomic orbital method for NMR chemical shift calculations. J Am Chem Soc 112:8251–8260 Additional Declarations There is NO Competing Interest. Supplementary Files Supportinginformationsilanesnaturecomm0909.docx Ambiphilic Hydrogen in Tri-substituted Silanes: Substituent- Driven Polarity Flip Confirmed by NMR Cite Share Download PDF Status: Published Journal Publication published 20 Mar, 2026 Read the published version in Communications Chemistry → Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. 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Hobza","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA+0lEQVRIiWNgGAWjYLCCBwwHGAwYGBgfANkJBkRpSYBoYTYgWQubBFFazNnPGD5IYLgjZ85/+Fk1T4VdnjkD88OPPxjs7HFpsezJMTZIYHhmbNlwzOw2z5nkYssGNmNpHoZkZlxaDA6kpUkkMBxO3HCwwew2b9uBxA0HeBikGRgOsOHUcv5Z+g+wlsPs34qhWph//mAAasSl5UbyMQawlmM8ZsxQLWwSPAwHJHD6ZcbjwxIJBoeNLXt4iiXnnElO3NnMZmbNY5CMM+TM+RMbP3yoOAwMseMbP7ypsEvczt78+OaPCtwhZoBEQgEzhgg2LaNgFIyCUTAK8AEAJRRVNDoGEZoAAAAASUVORK5CYII=","orcid":"https://orcid.org/0000-0001-5292-6719","institution":"Institute of Organic Chemistry and Biochemistry","correspondingAuthor":true,"prefix":"","firstName":"Pavel","middleName":"","lastName":"Hobza","suffix":""},{"id":520949383,"identity":"6d7436c7-5b40-4705-9a82-9e7a57f0fe05","order_by":1,"name":"Rabindranath Lo","email":"","orcid":"https://orcid.org/0000-0002-4436-3618","institution":"Institute of Organic Chemistry and Biochemistry 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06:14:25","extension":"html","order_by":11,"title":"","display":"","copyAsset":false,"role":"acdc-reference","size":137935,"visible":true,"origin":"","legend":"","description":"","filename":"earlyproof.html","url":"https://assets-eu.researchsquare.com/files/rs-7574907/v1/2f163c7b872b478a4462231d.html"},{"id":92381046,"identity":"70d6fab6-06ba-435d-8761-e5564e3e8fcf","added_by":"auto","created_at":"2025-09-29 06:14:21","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":761525,"visible":true,"origin":"","legend":"\u003cp\u003eThe molecular electrostatic potential surfaces of a) bromobenzene and b) Cl\u003csub\u003e3\u003c/sub\u003eSiH c) Et\u003csub\u003e3\u003c/sub\u003eSiH d) Cl\u003csub\u003e3\u003c/sub\u003eCH on the 0.001 au isodensity surface, both top and side view. The scale is in a.u.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-7574907/v1/d4f8995665533d340ccfc550.png"},{"id":92381078,"identity":"02508671-7ff0-4004-a39d-15a27eaa38c9","added_by":"auto","created_at":"2025-09-29 06:14:29","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":83457,"visible":true,"origin":"","legend":"\u003cp\u003eThe 1H NMR spectra of a) (C\u003csub\u003e6\u003c/sub\u003eF\u003csub\u003e5\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003eSi-H, b) (Me\u003csub\u003e3\u003c/sub\u003eSi)\u003csub\u003e3\u003c/sub\u003eSi-H in benzene and o-DCB medium.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-7574907/v1/b691075707900c056934520c.png"},{"id":92381071,"identity":"386d1550-f1c9-4c36-bd58-47f7faf1393f","added_by":"auto","created_at":"2025-09-29 06:14:29","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":78115,"visible":true,"origin":"","legend":"\u003cp\u003eCorrelation of dipole moment, chemical shift and \u003cem\u003eV\u003c/em\u003e\u003csub\u003es,max\u003c/sub\u003e\u0026nbsp; with solvent polarity for Cl\u003csub\u003e3\u003c/sub\u003eSiH and Et\u003csub\u003e3\u003c/sub\u003eSiH.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-7574907/v1/5b9858ffbae0b8980cca5e07.png"},{"id":109158098,"identity":"d2f5d1f6-ce1d-4c47-b976-b630a2efcd7b","added_by":"auto","created_at":"2026-05-13 07:08:19","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1524370,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7574907/v1/7088755a-a42b-4e6a-9f71-9f3cf965148b.pdf"},{"id":92381032,"identity":"c929bbc2-2a2f-491c-8b3f-a1af2f2d297c","added_by":"auto","created_at":"2025-09-29 06:14:16","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":2278118,"visible":true,"origin":"","legend":"Ambiphilic Hydrogen in Tri-substituted Silanes: Substituent- Driven Polarity Flip Confirmed by NMR","description":"","filename":"Supportinginformationsilanesnaturecomm0909.docx","url":"https://assets-eu.researchsquare.com/files/rs-7574907/v1/2c930d891d299c9160f87f1d.docx"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Ambiphilic Hydrogen in Trisubstituted Silanes: Substituent- Driven Polarity Flip Confirmed by NMR","fulltext":[{"header":"Introduction","content":"\u003cp\u003eThe distribution of electron density around a molecule plays a crucial role in determining its chemical reactivity and intermolecular interactions.\u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e,\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e Traditionally, this distribution is analyzed by calculating atomic charges using various theoretical models.\u003csup\u003e\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e,\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e\u003c/sup\u003e However, atomic charges are only local properties and are not easily observable quantities. In contrast, the molecular electrostatic potential (ESP), which takes into account both the nuclear charges and the electron densities of all atoms in a molecule, is a global, easily observable property that provides a more comprehensive and physically meaningful description.\u003csup\u003e\u003cspan additionalcitationids=\"CR6 CR7 CR8 CR9 CR10 CR11\" citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e\u003cp\u003eA comprehensive understanding of a molecule\u0026rsquo;s reactivity and its propensity for noncovalent interactions requires considering both atomic partial charges and the overall topology of the ESP. Generally, the regions of maximum and minimum ESP (\u003cem\u003eV\u003c/em\u003e\u003csub\u003eₛ,max\u003c/sub\u003e and \u003cem\u003eV\u003c/em\u003e\u003csub\u003eₛ,min\u003c/sub\u003e) coincide with the most positive and negative atomic charges, respectively. Notable exceptions exist, however, where atomic charges fail to capture the true ESP distribution. In such cases, it is the ESP, not the atomic charges, that determines whether a molecule behaves as an electrophile or a nucleophile.\u003c/p\u003e\u003cp\u003eOne of the clearest examples of this mismatch is the anisotropic electron density around a halogen covalently bonded to carbon (R\u0026ndash;X), which creates a positive ESP region (the σ-hole) opposite the R\u0026ndash;X bond.\u003csup\u003e\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u003c/sup\u003e This concept was extensively developed by Peter Politzer, Jane S. Murray, and Timothy Clark, who advocated the umbrella term \u0026ldquo;σ-hole bonding\u0026rdquo; for interactions involving such regions, encompassing halogen, chalcogen, pnictogen, tetrel, and triel bonds.\u003csup\u003e\u003cspan additionalcitationids=\"CR15\" citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e\u003cp\u003eThe σ-hole concept was introduced to rationalize the counterintuitive electrophilicity of halogens covalently bound to carbon. Despite their higher electronegativity and the resulting net negative atomic charge, these halogens often act as electrophiles. A positive σ-hole resolves the paradox, a localized maximum in the ESP along the extension of the R\u0026ndash;X bond, which engages attractively with electron-rich sites. This behavior highlights the limitations of atom-centered charges and underscores the importance of ESP in accurately describing reactivity and noncovalent interactions.\u003csup\u003e\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e\u003cp\u003eThe situation for chemical bonds involving the lightest element, hydrogen, is notably different. In bonds such as F-H, O-H, N-H, and also C-H, the heavier atom (Y) is generally more electronegative than hydrogen. Consequently, the Y-H bond is polarized towards the heavier atom (Y), rendering the hydrogen atom partially positive, or protic. This protic nature of hydrogen remains generally consistent regardless of the substituents attached to the heavy atom or the broader molecular environment.\u003c/p\u003e\u003cp\u003eBy contrast, for the heavier Group 14 elements, i.e., silicon, germanium, and tin, the trend reverses. Since these atoms are more electropositive than hydrogen (Pauling electronegativities: Si 1.74, Ge 2.02, Sn 1.72 vs H 2.20), Y\u0026ndash;H bonds are polarized toward hydrogen, giving H a negative partial charge, making them hydridic in nature. Such hydridic hydrogen forms non-covalent complexes with various types of electron acceptors, including positive σ-, π-, and p-holes confirmed by theoretical and experimental studies.\u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e,\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u003c/sup\u003e Furthermore, silanes act as a versatile hydride source for catalytic reactions.\u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u003c/sup\u003e Crucially, however, a negative atomic charge on hydrogen does not necessarily imply a negative ESP in its vicinity. Substituents on the tetrel center might markedly reshape the local ESP at H, and even invert its sign.\u003c/p\u003e\u003cp\u003eIn unsubstituted silane (SiH₄), hydrogen is hydridic (q\u0026thinsp;=\u0026thinsp;\u0026minus;\u0026thinsp;0.141), yet the corresponding \u003cem\u003eV\u003c/em\u003eₛ,\u003csub\u003emax\u003c/sub\u003e in the vicinity of H is slightly positive (+\u0026thinsp;1.73).\u003csup\u003e20\u003c/sup\u003e In substituted silanes, the hydrogen typically retains a negative partial charge, but the ESP near H can change dramatically with the nature of the substituents. Consequently, the region around H may be either ESP-positive or ESP-negative, enabling the silane hydrogen to behave as an electrophile or a nucleophile under different conditions.\u003c/p\u003e\u003cp\u003eFor completeness, we also examined other hydrogen-containing bonds that could exhibit related behavior. In Al\u0026ndash;H bonds, the strong electropositivity of aluminum renders hydrogen hydridic, and the ESP near H can switch sign with substitution, closely paralleling the Si\u0026ndash;H case. By contrast, C\u0026ndash;H and P\u0026ndash;H bonds remain consistently protic with positive ESP near hydrogen, regardless of the substitutions considered. Thus, within the neutral molecules, silicon represents a rare nonmetal capable of displaying ambiphilic behavior at the Y\u0026ndash;H bond.\u003c/p\u003e\u003cp\u003eThis study investigates the electronic structure and ambiphilic behavior of Si-H in trisubstituted silanes in the gas phase and in two solvents, benzene (BEN) and o-dichlorobenzene (o-DCB), with computational results complemented and validated by experimental NMR spectroscopy.\u003c/p\u003e"},{"header":"Results and Discussion","content":"\u003cp\u003eThe structures and charge distributions of trisubstituted silanes were investigated by DFT at the PBE0-D3/def2-TZVPP level. Calculations were performed in the gas phase and in BEN and o-DCB using a polarizable continuum model (dielectric constants 2.27 and 9.99 for BEN and o-DCB, respectively). Substituents spanned electron-withdrawing groups (EWGs: F, Cl, Br, CF₃, CN, NO₂, C\u003csub\u003e6\u003c/sub\u003eF\u003csub\u003e5\u003c/sub\u003e) to electron-donating groups (EDGs: Me, Et, \u003cem\u003ei\u003c/em\u003ePr, Ph, NH₂, NMe₂). For each silane, we determined atomic charges and the extrema of the electrostatic potential on the molecular surface (\u003cem\u003eV\u003c/em\u003eₛ,\u003csub\u003emax,\u003c/sub\u003e \u003cem\u003eV\u003c/em\u003eₛ,\u003csub\u003emin\u003c/sub\u003e; Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). Optimized structures are shown in Figure \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e. We first discuss hydrogen atomic charges computed using NBO (Natural Bond Orbital), Mulliken, Hirshfeld, ADCH (atomic dipole moment corrected Hirshfeld) and CM5 (Charge Model 5) schemes (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). NBO yields the largest magnitudes, whereas Mulliken and Hirshfeld give smaller and mutually similar values. In BEN and o-DCB, hydrogen charges become less negative for EWG-substituted silanes and more negative for EDG-substituted silanes. Notably, for EWG-substituted systems, the hydrogen charges calculated from NBO,\u003csup\u003e\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e\u003c/sup\u003e Mulliken, Hirshfeld\u003csup\u003e\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u003c/sup\u003e at hydridic H do not correlate with the ESP, whereas for EDG-substituted silanes, they correlate well. However, the partial charges derived from the ADCH\u003csup\u003e\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u003c/sup\u003e and CM5\u003csup\u003e24\u003c/sup\u003e methods exhibit a comparatively stronger correlation with the ESP in EWG-substituted systems.\u003csup\u003e\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e\u003c/sup\u003e Both methods employ Hirshfeld population analysis, which partitions the molecular electron density to determine partial atomic charges.\u003c/p\u003e\u003cp\u003eA central result is the mismatch that can arise between local atomic charge and the global electrostatic potential (ESP) at hydrogen. For EDG-substituted silanes, however, the picture is straightforward: all charge schemes (NBO, Mulliken, Hirshfeld, ADCH, CM5) assign a negative partial charge to H, and the surface ESP at H is likewise negative. Accordingly, H behaves as a nucleophilic, hydridic site. The ESP around H is anisotropic: it is least negative at the axial \u0026ldquo;pole\u0026rdquo; along the Si\u0026ndash;H bond and most negative around the equatorial \u0026ldquo;belt\u0026rdquo; (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e), where \u003cem\u003eV\u003c/em\u003e\u003csub\u003eₛ,min\u003c/sub\u003e is located (see later).\u003c/p\u003e\u003cp\u003eFor EWG-substituted silanes, an intriguing inversion appears. Most of the charge-partitioning schemes still assign H a negative partial charge, seemingly indicating a nucleophilic site, but the surface ESP near H tells a different story: \u003cem\u003eV\u003c/em\u003eₛ,\u003csub\u003emax\u003c/sub\u003e along the Si\u0026ndash;H axis is positive, marking H as electrophilic. Strong electron withdrawal by the substituents, together with the resulting positive polarization of the silicon center, depletes electron density in the Si\u0026ndash;H bond direction and creates a σ-hole\u0026ndash;like positive lobe at H. The local charge on H remains negative because, within the Si\u0026ndash;H bond, H still integrates to slightly more electron density than a neutral atom. Nonetheless, the global electrostatic environment is dominated by the surrounding framework, so these hydrogens behave as electrophiles in their interactions.\u003c/p\u003e\u003cp\u003eThe data make this clear: in EWG-substituted silanes, \u003cem\u003eV\u003c/em\u003eₛ,\u003csub\u003emax\u003c/sub\u003e at H is positive, signaling an electron-poor region, even though the atomic charge on H is negative. Crucially, it is the sign of the ESP at H, not q(H), that tracks reactivity. A negative ESP at H (typical for EDG-substituted silanes) corresponds to a nucleophilic, hydridic hydrogen capable of donating electron density. A positive ESP at H (typical for EWG-substituted silanes) marks an electrophilic, electron-deficient hydrogen, akin to a protic site. Relying on local charges alone would incorrectly label all these silanes as bearing nucleophilic (hydridic) hydrogens; the ESP analysis instead reveals a sharp division, EDG-silanes maintain nucleophilic H, whereas EWG-silanes flip to electrophilic H.\u003c/p\u003e\u003cp\u003eA natural question is whether the ambiphilic behavior observed for Si\u0026ndash;H, in which substitution toggles the hydrogen between nucleophilic and electrophilic character, also occurs for other Y\u0026ndash;H bonds, particularly those with small electronegativity differences between Y and H. Tables S1-S6 compile partial atomic charges and ESP values (PBE0-D3/def2-TZVPP) for X₃C\u0026ndash;H, X₃Ge\u0026ndash;H, X₃Sn\u0026ndash;H, X₃Pb\u0026ndash;H, X₂Al\u0026ndash;H, and X₂P\u0026ndash;H with both EWG and EDG substituents. Only carbon is more electronegative than hydrogen; all other elements considered are more electropositive. Using Δχ\u0026thinsp;\u0026equiv;\u0026thinsp;χ(H) \u0026minus; χ(X), the differences are \u0026minus;\u0026thinsp;0.30 (C), +\u0026thinsp;0.46 (Si), +\u0026thinsp;0.18 (Ge), +\u0026thinsp;0.48 (Sn), +\u0026thinsp;0.64 (Pb), +\u0026thinsp;0.73 (Al), and +\u0026thinsp;0.14 (P).\u003c/p\u003e\u003cp\u003eFor X₃C\u0026ndash;H, hydrogen is protic for all substituents considered and the ESP at H is positive, consistent with electrophilic behavior. X₂P\u0026ndash;H systems likewise show systematically positive ESP at H and are electrophilic. Upon moving to solvent (BEN, o-DCB), both q(H) and \u003cem\u003eV\u003c/em\u003eₛ,\u003csub\u003emax\u003c/sub\u003e shift to more positive values in these two families.\u003c/p\u003e\u003cp\u003eX₂Al\u0026ndash;H behaves differently. Here, H is uniformly hydridic, yet ESP at H depends on substitution: it is positive for EWG-substituted alanes and negative for EDG-substituted alanes, mirroring the X₃Si\u0026ndash;H case. Accordingly, EDG-substituted alanes feature nucleophilic H, whereas EWG-substituted alanes display electrophilic H. Increasing solvent polarity drives ESP at H more negative for EDG cases and more positive for EWG cases. Solvent effects were not considered in all remaining molecules, and only the gas phase calculations were performed.\u003c/p\u003e\u003cp\u003e\u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e\u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e\u003cdiv class=\"CaptionContent\"\u003e\u003cp\u003eThe calculated Mulliken, Natural Bond Orbital, Hirshfeld, ADCH and CM5 charges (in e) on the H and Si atoms of X\u003csub\u003e3\u003c/sub\u003eSi-H in various medium at the PBE0-D3/def2-TZVPP level of theory. The extrema of the ESP on the molecular surface in the vicinity of H atom given in kcal/mol.\u003c/p\u003e\u003c/div\u003e\u003c/caption\u003e\u003ccolgroup cols=\"13\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c9\" colnum=\"9\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c10\" colnum=\"10\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c11\" colnum=\"11\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c12\" colnum=\"12\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c13\" colnum=\"13\"\u003e\u003c/div\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003eX\u003csub\u003e3\u003c/sub\u003eSi-H\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e\u003cp\u003eMulliken\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colspan=\"2\" nameend=\"c6\" namest=\"c5\"\u003e\u003cp\u003eNBO\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colspan=\"2\" nameend=\"c8\" namest=\"c7\"\u003e\u003cp\u003eHirshfeld\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colspan=\"2\" nameend=\"c10\" namest=\"c9\"\u003e\u003cp\u003eADCH\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colspan=\"2\" nameend=\"c12\" namest=\"c11\"\u003e\u003cp\u003eCM5\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003eESP\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003eH\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003eSi\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003eH\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003eSi\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003eH\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003eSi\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003eH\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003eSi\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003eH\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003eSi\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\" morerows=\"2\" rowspan=\"3\"\u003e\u003cp\u003eSiH\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eGas\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e-0.047\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e0.187\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e-0.141\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e0.562\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e-0.067\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e0.267\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e-0.030\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e0.118\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e0.013\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e-0.052\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e1.73\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eBEN\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e-0.047\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e0.190\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e-0.141\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e0.563\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e-0.067\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e0.267\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e-0.030\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e0.119\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e0.013\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e-0.052\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e1.71\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eo-DCB\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e-0.048\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e0.192\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e-0.141\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e0.564\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e-0.067\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e0.267\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e-0.030\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e0.119\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e0.013\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e-0.052\u003c/p\u003e\u003c/td\u003e\u003ctd 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align=\"left\" colname=\"c10\"\u003e\u003cp\u003e0.541\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e0.045\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e0.438\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e16.10\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eBEN\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e-0.056\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e0.932\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e-0.263\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e2.183\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e-0.034\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" 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rowspan=\"3\"\u003e\u003cp\u003e(Me\u003csub\u003e3\u003c/sub\u003eSi)\u003csub\u003e3\u003c/sub\u003eSiH\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eGas\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e-0.081\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e-0.043\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e-0.093\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e-0.204\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e-0.077\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e0.021\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e-0.028\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e-0.091\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" 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colname=\"c3\"\u003e\u003cp\u003e-0.129\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e0.542\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e-0.255\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e1.810\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e-0.099\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e0.348\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e-0.082\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e0.420\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-0.009\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e0.337\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e-13.14\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eBEN\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e-0.140\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e0.550\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e-0.263\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e1.809\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e-0.104\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e0.342\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e-0.092\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e0.444\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-0.015\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e0.330\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e-14.86\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eo-DCB\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e-0.173\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e0.588\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e-0.282\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e1.825\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e-0.117\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e0.341\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e-0.096\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e0.482\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-0.030\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e0.328\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e-13.75\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\" morerows=\"2\" rowspan=\"3\"\u003e\u003cp\u003e(Me\u003csub\u003e2\u003c/sub\u003eN)\u003csub\u003e3\u003c/sub\u003eSiH\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eGas\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e-0.113\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e0.262\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e-0.252\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e1.899\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e-0.093\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e0.357\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e-0.076\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e0.292\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-0.003\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e0.347\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e-10.50\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eBEN\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e-0.122\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e0.270\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e-0.259\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e1.902\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e-0.099\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e0.352\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e-0.086\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e0.297\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-0.009\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e0.342\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e-12.57\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eo-DCB\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e-0.129\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e0.273\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e-0.265\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e1.905\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e-0.103\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e0.347\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e-0.094\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e0.300\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-0.014\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e0.338\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e-14.66\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/colgroup\u003e\u003c/table\u003e\u003c/div\u003e\u003c/p\u003e\u003cp\u003e\u003csup\u003ea\u003c/sup\u003e The \u003cem\u003eV\u003c/em\u003e\u003csub\u003es,min\u003c/sub\u003e of H atom on the extension of Si-H.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003e\u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e\u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e\u003cdiv class=\"CaptionContent\"\u003e\u003cp\u003eThe proton chemical shifts of silanes, as well as their corresponding differences in two solvents, calculated at the PBE0-D3/def2-TZVPP level of theory using the COSMO continuum solvation model in benzene and o-DCB. The experimental proton chemical shifts of the silanes are also provided.\u003c/p\u003e\u003c/div\u003e\u003c/caption\u003e\u003ccolgroup cols=\"6\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003eSilane\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003eMedium\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e\u003cp\u003eCalculated \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH chemical shifts\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colspan=\"2\" nameend=\"c6\" namest=\"c5\"\u003e\u003cp\u003eExperimental \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH chemical shifts\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e\u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH δ ppm\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003eRelative Δδ \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH ppm\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e\u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH δ ppm\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003eRelative Δδ \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH ppm\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003e(C\u003csub\u003e6\u003c/sub\u003eF\u003csub\u003e5\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003eSi-H\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eBEN\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e6.609\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003e0.002\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e5.81\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003e0.14\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eo-DCB\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e6.611\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e5.95\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003e(Me\u003csub\u003e3\u003c/sub\u003eSi)\u003csub\u003e3\u003c/sub\u003eSi-H\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eBEN\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e2.635\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003e-0.121\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e2.54\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003e-0.23\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eo-DCB\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e2.514\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e2.31\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003eEt\u003csub\u003e3\u003c/sub\u003eSiH\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eBEN\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e4.017\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003e-0.089\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e3.90\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003e-0.21\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eo-DCB\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e3.928\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e3.69\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003ePh\u003csub\u003e3\u003c/sub\u003eSiH\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eBEN\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e6.203\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003e-0.037\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e5.71\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003e-0.21\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eo-DCB\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e6.166\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e5.50\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/colgroup\u003e\u003c/table\u003e\u003c/div\u003e\u003c/p\u003e\u003cp\u003e\u003csup\u003ea 1H NMR of TMS taken as a reference with the isotropic shielding value of 31.506 ppm\u003c/sup\u003e.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eThese results highlight the superiority of a global, ESP-based description over purely local charge analyses for understanding and predicting reactivity. In particular, ESP mapping accurately distinguishes silanes that act as hydride donors from those exhibiting protic, electrophilic behavior, a distinction that partial atomic charges alone fail to capture. While local charge analysis would suggest uniformly nucleophilic behavior for all silanes, a global ESP-based approach correctly predicts electrophilic behavior for EWG-substituted silanes and nucleophilic behavior for EDG-substituted silanes. To validate this, we examined silanes in two aprotic solvents, BEN and o-DCB. Upon moving from the gas phase to solvent, \u003cem\u003eV\u003c/em\u003e\u003csub\u003eₛ,max\u003c/sub\u003e at H shifts more positive for EWG-substituted silanes and more negative for EDG-substituted silanes.\u003c/p\u003e\u003cp\u003eTo support these theoretical trends, we recorded \u0026sup1;H NMR spectra for four commercially available silanes, ((C₆F₅)₃Si\u0026ndash;H, (Me₃Si)₃Si\u0026ndash;H, Et₃SiH, and Ph₃SiH) in BEN and o-DCB. As shown in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, (C₆F₅)₃Si\u0026ndash;H exhibits a positive ESP at H, whereas the others show a negative ESP at H. The experimental chemical shifts are summarized in Tables\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e and S7 and compared with values computed at the PBE0-D3/def2-TZVPP\u003csup\u003e26\u0026ndash;28\u003c/sup\u003e level using the COSMO\u003csup\u003e\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e\u003c/sup\u003e continuum model. Experimental details and individual spectra are provided in the Supporting Information (Figures S2\u0026ndash;S9).\u003c/p\u003e\u003cp\u003eProtic hydrogens typically exhibit modest, polarity-dependent solvent shifts and tend to move downfield as solvent polarity increases.\u003csup\u003e\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e,\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u003c/sup\u003e We observe this behavior for the EWG-substituted silane (C₆F₅)₃Si\u0026ndash;H: \u003cem\u003eV\u003c/em\u003e\u003csub\u003eₛ,max\u003c/sub\u003e at H becomes more positive upon going from BEN to o-DCB, and a downfield shift of the \u0026sup1;H resonance (Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e). In contrast, EDG-substituted silanes ((Me₃Si)₃Si\u0026ndash;H, Et₃SiH, and Ph₃SiH) show the opposite trend (Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e), in line with their negative \u003cem\u003eV\u003c/em\u003e\u003csub\u003eₛ,max\u003c/sub\u003e values: increasing solvent polarity drives \u003cem\u003eV\u003c/em\u003e\u003csub\u003eₛ,max\u003c/sub\u003e more negative and shifts the \u0026sup1;H signal upfield. In NMR, the observed chemical shift (δ) depends on how much the local electrons oppose the external magnetic field (B₀). A more negative ESP at H means the region around H is richer in electron density (from bond polarization and substituent effects). This increased local electron density can partially shield the nucleus from B₀. When electron density circulates under B₀, it generates an induced magnetic field (B\u003csub\u003eind\u003c/sub\u003e) that opposes B₀ at the nucleus. Thus, higher electron density reduces the effective magnetic field at the nucleus (B\u003csub\u003eeff\u003c/sub\u003e = B₀ \u0026ndash; B\u003csub\u003eind\u003c/sub\u003e). This means the nucleus resonates at a higher field strength (upfield) and shows a lower δ value (shielding). In contrast, a positive ESP at H means electron density is drawn away, leaving H electron-poor. With fewer shielding electrons, the nucleus feels more of B₀. This results in deshielding or downfield shift (larger δ) of H. Atomic charges are intrinsically local properties, whereas both the ESP and NMR chemical shifts capture not only local electron density but also the broader molecular environment and intermolecular influences. Thus, ESP and NMR chemical shifts show consistent trends and reinforce each other, in line with the expectation. Since both BEN and o-DCB are aromatic, differential ring-current effects are minimized, so the observed chemical-shift changes can be attributed primarily to solvent polarity.\u003c/p\u003e\u003cp\u003e\u0026sup1;H NMR measurements in BEN and o-DCB corroborate the divergent reactivity of EWG- and EDG-substituted silanes, supporting the ESP-based, non-local description of charge distribution.\u003c/p\u003e\u003cp\u003eA comprehensive computational analysis was performed for Et₃SiH and trichlorosilane in the gas phase and in four additional solvents: chloroform, acetone, acetonitrile, and DMSO. Because these calculations used the implicit COSMO model, solvent effects are governed solely by the dielectric constant (ε); features such as protic/aprotic character and aromaticity are not represented. For EWG- versus EDG-substituted silanes, the influence of solvent polarity on \u0026sup1;H chemical shifts, \u003cem\u003eV\u003c/em\u003e\u003csub\u003eₛ,max\u003c/sub\u003e values, and dipole moments follows opposite trends (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). In the EDG-substituted silane Et₃SiH, increasing ε decreases both \u003cem\u003eV\u003c/em\u003e\u003csub\u003eₛ,max\u003c/sub\u003e, and the dipole moment, accompanied by an upfield shift of the Si\u0026ndash;H \u0026sup1;H resonance. In contrast, in the EWG-substituted trichlorosilane, increasing ε raises \u003cem\u003eVₛ\u003c/em\u003e,\u003csub\u003e\u003cem\u003emax\u003c/em\u003e\u003c/sub\u003e, and the dipole moment and produces a downfield shift of the Si\u0026ndash;H \u0026sup1;H signal. These opposing behaviors reflect the positive ESP induced by EWGs. Because the dipole vectors of EWG- and EDG-substituted silanes are oriented in opposite directions, we plot dipole moments for the EDG cases with a negative sign for consistency. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, solvent effects are most pronounced at low ε and become negligible at higher ε.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eWe have shown that in EWG-substituted silanes the \u003cem\u003eV\u003c/em\u003e\u003csub\u003eₛ,max\u003c/sub\u003e near H becomes positive. This resembles the positive σ-hole observed for halogens covalently bonded to carbon. Figure\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e illustrates the parallel by comparing the anisotropic ESP in bromobenzene (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea) and trichlorosilane (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb). In bromobenzene, although Br bears a net negative atomic charge, a pronounced positive region, the σ-hole, appears along the extension of the C\u0026ndash;Br bond, while a belt of negative potential lies perpendicular to this axis. Here, within the σ-hole, the ESP is uniformly positive relative to its surroundings. Trichlorosilane shows an analogous anisotropy around the hydridic hydrogen: despite a negative partial charge on H, a positive ESP \u0026ldquo;cap\u0026rdquo; is found along the Si\u0026ndash;H axis (the pole), and even the equatorial belt remains positive (\u0026thinsp;\u0026asymp;\u0026thinsp;+\u0026thinsp;11.1) though less than at the pole (\u0026thinsp;\u0026asymp;\u0026thinsp;+\u0026thinsp;12.9). Consequently, the Si\u0026ndash;H bond in such silanes acts exclusively as an electrophilic site.\u003c/p\u003e\u003cp\u003eIn halogens such as bromine, the σ-hole arises from an anisotropic electron distribution associated with the presence of lone pairs, allowing the atom to act as an electrophile along the bond axis and as a nucleophile in the perpendicular belt. This can be rationalized either as a depletion of electron density along the C\u0026ndash;Br extension or, qualitatively, as a change in hybridization (sp\u0026sup3; \u0026rarr; sp\u0026sup2;) that allocates five valence electrons to two lone pairs and the C\u0026ndash;Br σ bond, leaving the third lone pair empty. This region along the bond axis constitutes the σ-hole.\u003c/p\u003e\u003cp\u003eHydrogen, by contrast, has no core shell or lone pairs to redistribute; its ESP anisotropy in substituted silanes stems from the collective molecular electron distribution rather than depletion of a localized pair. In triethylsilane (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ec), H carries a negative partial charge and the nearby ESP is negative and nearly uniform; a slight anisotropy remains, with the pole (\u0026thinsp;\u0026asymp;\u0026thinsp;\u0026minus;\u0026thinsp;8.3) being marginally less negative (i.e., more positive) than the belt (\u0026thinsp;\u0026asymp;\u0026thinsp;\u0026minus;\u0026thinsp;8.6). For comparison, chloroform (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ed) features a protic hydrogen with a positive ESP in its vicinity.\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eIn summary, the molecular electrostatic potential, not local atomic charges, is the reliable descriptor for predicting and rationalizing the behavior of the Si-H of trisubstituted silanes. Across PBE0-D3/def2-TZVPP computations in the gas phase and in benzene and o-dichlorobenzene, corroborated by solvent-dependent ¹H NMR shifts, we find a clear, substituent-controlled dichotomy:\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cul\u003e\u003cli\u003e\u003cp\u003eEDG-substituted silanes: Hydrogens are hydridic and nucleophilic: q(H) \u0026lt; 0 and the surface ESP near H is negative. Increasing solvent polarity drives ESP more negative and shifts the Si–H resonance upfield, consistent with an electron-rich H.\u003c/p\u003e\u003c/li\u003e\u003cli\u003e\u003cp\u003eEWG-substituted silanes: Hydrogens are hydridic yet electrophilic: q(H) \u0026lt; 0 but the surface ESP near H is positive. Higher dielectric media make ESP more positive and shift the Si–H resonance downfield, revealing an electron-poor H. Local charges alone would incorrectly predict uniform nucleophilicity across both series.\u003c/p\u003e\u003c/li\u003e\u003c/ul\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eThus, ESP provides a robust, transferable predictor of Si–H reactivity.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cul\u003e\u003cli\u003e\u003cp\u003eσ-hole analogy: The positive region near H in EWG-substituted silanes is σ-hole-like in directionality but does not arise from lone-pair depletion on hydrogen; it reflects a collective, molecular ESP effect.\u003c/p\u003e\u003c/li\u003e\u003c/ul\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eGeneralization to other Y–H bonds with small Y/H electronegativity gaps reveals consistent behavior: X₃C–H and X₂P–H remain protic with positive ESP at H (electrophilic) across all cases studied, whereas X₂Al–H mirrors Si–H by exhibiting an ESP-governed switch. Si–H is unusual among neutral nonmetals for its ability to exhibit pronounced ambiphilic behavior. Thus, global ESP features—particularly \u003cem\u003eV\u003c/em\u003eₛ\u003csub\u003e,max,\u003c/sub\u003e \u003cem\u003eV\u003c/em\u003eₛ\u003csub\u003e,min\u003c/sub\u003e at H—outperform local partial charges as predictors of electrophilic versus nucleophilic character. These insights provide practical guidelines for engineering noncovalent interactions, tuning Si–H reactivity in synthesis and catalysis, and avoiding misassignments that arise from relying solely on local atomic charges while neglecting the global electrostatic field.\u003c/p\u003e\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e\u003cdiv id=\"Sec4\" class=\"Section3\"\u003e\u003c/div\u003e\u003c/div\u003e"},{"header":"Methods","content":"\u003ch2\u003eComputational details\u003c/h2\u003e\u003cp\u003eAll molecular geometries were optimized using density functional theory (DFT) at the PBE0-D3 \u003csup\u003e26,27\u003c/sup\u003e level with the def2-TZVPP basis set.\u003csup\u003e\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e\u003c/sup\u003e Vibrational frequency calculations were carried out at the same level to verify that the optimized structures correspond to local minima (no imaginary frequencies). Solvent effects of benzene and o-dichlorobenzene were included during geometry optimizations via the COSMO continuum solvation model.\u003csup\u003e\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e\u003c/sup\u003e All computations were performed using the Gaussian 16 software package.\u003csup\u003e\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u003c/sup\u003e Atomic partial charges were determined using Natural Bond Order (NBO),\u003csup\u003e\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e\u003c/sup\u003e Hirshfeld,\u003csup\u003e\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u003c/sup\u003e and charge model 5 (CM5) methods\u003csup\u003e\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u003c/sup\u003e within Gaussian 16. Additionally, atomic dipole–corrected Hirshfeld (ADCH) charges\u003csup\u003e\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e\u003c/sup\u003e and the maximum electrostatic potential (\u003cem\u003eV\u003c/em\u003e\u003csub\u003es,max\u003c/sub\u003e) near hydrogen atoms were calculated using the Multiwfn program.\u003csup\u003e\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e\u003c/sup\u003e NMR chemical shifts for the optimized geometries were calculated using the Gauge-Including Atomic Orbital (GIAO) method,\u003csup\u003e\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e\u003c/sup\u003e with tetramethylsilane (TMS) employed as the reference standard.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003ch2\u003eCompeting interests\u003c/h2\u003e\u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e\u003c/p\u003e\u003ch2\u003eAuthor contributions\u003c/h2\u003e\u003cp\u003eP.H. supervised the project. R.L. and D. M. carried out the quantum chemical calculations. V. H. performed the experiments. All authors discussed the results and commented on the manuscript.\u003c/p\u003e\u003ch2\u003eAcknowledgments\u003c/h2\u003e\u003cp\u003eThis article has been produced with the financial support of the European Union under the REFRESH \u0026ndash; Research Excellence for Region Sustainability and High-tech Industries project number CZ.10.03.01/00/22_003/0000048 via the Operational Programme Just Transition (P.H.). V.H. acknowledges the support from ERDF/ESF Project TECHSCALE (Grant CZ.02.01.01/00/22_008/0004587).\u003c/p\u003e\u003ch2\u003eData Availability Statement\u003c/h2\u003e\u003cp\u003eThe data that support the findings of this study are available in the supporting information of this article. The publication data will be made available at ZENODO after manuscript acceptance.\u003c/p\u003e\n\u003cp\u003eAdditional Information\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSupplementary information\u003c/strong\u003e The online version contains supplementary material available at\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eFeynman RP (1939) Forces in Molecules. Phys Rev 56:340\u0026ndash;343\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eSuresh CH, Anila S (2023) Molecular Electrostatic Potential Topology Analysis of Noncovalent Interactions. Acc Chem Res 56:1884\u0026ndash;1895\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eCho M et al (2020) The Atomic Partial Charges Arboretum: Trying to See the Forest for the Trees. \u003cem\u003eChemPhysChem\u003c/em\u003e 21, 688\u0026ndash;696\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eMahmoudi S et al (2025) Experimental determination of partial charges with electron diffraction. Nature. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003e10.1038/s41586-025-09405-0\u003c/span\u003e\u003cspan address=\"10.1038/s41586-025-09405-0\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eMurray JS, Politzer P (2011) The electrostatic potential: an overview. WIREs Comput Mol Sci 1:153\u0026ndash;163\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eBulat FA, Toro-Labb\u0026eacute; A, Brinck T, Murray JS, Politzer P (2010) Quantitative analysis of molecular surfaces: areas, volumes, electrostatic potentials and average local ionization energies. J Mol Model 16:1679\u0026ndash;1691\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003ePolitzer P, Landry SJ, Waernheim T (1982) Proposed procedure for using electrostatic potentials to predict and interpret nucleophilic processes. J Phys Chem 86:4767\u0026ndash;4771\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003ePolitzer P, Laurence PR, Jayasuriya K (1985) Molecular electrostatic potentials: an effective tool for the elucidation of biochemical phenomena. Environ Health Perspect 61:191\u0026ndash;202\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eBrinck T, Murray JS, Politzer P (1992) Surface electrostatic potentials of halogenated methanes as indicators of directional intermolecular interactions. Int J Quantum Chem 44:57\u0026ndash;64\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eSuresh CH, Remya GS, Anjalikrishna PK (2022) Molecular electrostatic potential analysis: A powerful tool to interpret and predict chemical reactivity. WIREs Comput Mol Sci 12:e1601\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eHaritha M, Suresh CH (2023) The fundamental nature and importance of electrostatic potential in hydrogen bond formation: a case study of heterocycles frequently observed in drugs. New J Chem 47:17323\u0026ndash;17332\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eShin D, Jung Y (2022) Molecular electrostatic potential as a general and versatile indicator for electronic substituent effects: statistical analysis and applications. Phys Chem Chem Phys 24:25740\u0026ndash;25752\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eMallada B et al (2021) Real-space imaging of anisotropic charge of σ-hole by means of Kelvin probe force microscopy. Science 374:863\u0026ndash;867\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003ePolitzer P, Murray JS, Clark T (2013) Halogen bonding and other σ-hole interactions: a perspective. Phys Chem Chem Phys 15:11178\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eClark T, Hennemann M, Murray JS, Politzer P (2007) Halogen bonding: the σ-hole: Proceedings of Modeling interactions in biomolecules II, Prague, September 5th\u0026ndash;9th, 2005. \u003cem\u003eJ Mol Model\u003c/em\u003e 13, 291\u0026ndash;296\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eKol\u0026aacute;ř MH, Hobza P (2016) Computer Modeling of Halogen Bonds and Other σ-Hole Interactions. Chem Rev 116:5155\u0026ndash;5187\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eManna D et al (2025) Beyond Deshielding: NMR Evidence of Shielding in Hydridic and Protonic Hydrogen Bonds. J Chem Theory Comput 21:7495\u0026ndash;7502\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eCiviš S et al (2023) Hydrogen Bonding with Hydridic Hydrogen\u0026ndash;Experimental Low-Temperature IR and Computational Study: Is a Revised Definition of Hydrogen Bonding Appropriate? J Am Chem Soc 145:8550\u0026ndash;8559\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eMirza YK, Bera PS, Mohite SB, Pandey AK, Bera M (2024) Silanes as a versatile hydride source for Ni\u0026ndash;H catalysis: a promising tool for π-hydro functionalization. Org Chem Front 11:4290\u0026ndash;4317\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eScheiner S (2025) Lower limits on hydrogen bond strength. Charge of bridging H atom. Phys Chem Chem Phys 27:10283\u0026ndash;10290\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eReed AE, Curtiss LA, Weinhold F (1988) Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint. Chem Rev 88:899\u0026ndash;926\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eHirshfeld FL (1977) Bonded-atom fragments for describing molecular charge densities. Theoret Chim Acta 44:129\u0026ndash;138\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eLu T, Chen F, ATOMIC DIPOLE MOMENT (2012) CORRECTED HIRSHFELD POPULATION METHOD. J Theor Comput Chem 11:163\u0026ndash;183\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eMarenich AV, Jerome SV, Cramer CJ, Truhlar DG (2012) Charge Model 5: An Extension of Hirshfeld Population Analysis for the Accurate Description of Molecular Interactions in Gaseous and Condensed Phases. J Chem Theory Comput 8:527\u0026ndash;541\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eQin L et al (2024) The strongest dative bond in main-group compounds. Theoretical study of OAeF\u003csup\u003e\u0026ndash;\u003c/sup\u003e (Ae\u0026thinsp;=\u0026thinsp;Be\u0026ndash;Ba). Phys Chem Chem Phys 26:24294\u0026ndash;24313\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eAdamo C, Barone V (1999) Toward reliable density functional methods without adjustable parameters: The PBE0 model. J Chem Phys 110:6158\u0026ndash;6170\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eGrimme S, Antony J, Ehrlich S, Krieg H (2010) A consistent and accurate \u003cem\u003eab initio\u003c/em\u003e parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J Chem Phys 132:154104\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eWeigend F, Ahlrichs R (2005) Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. Phys Chem Chem Phys 7:3297\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eKlamt A, Sch\u0026uuml;\u0026uuml;rmann G (1993) COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient. J Chem Soc Perkin Trans 2:799\u0026ndash;805. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003e10.1039/P29930000799\u003c/span\u003e\u003cspan address=\"10.1039/P29930000799\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eFulmer GR et al (2010) NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the Organometallic Chemist. Organometallics 29:2176\u0026ndash;2179\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eGoyary S, Sarmah MJ, Goswami HP, Nath N (2024) Solvent-induced 1H NMR chemical shifts of annulenes. Comput Theor Chem 1236:114601\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eFrisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Petersson GA, Nakatsuji H, Li X, Caricato M, Marenich AV, Bloino J, Janesko BG, Gomperts R, Mennucci B, Hratchian HP, Ortiz JV, Izmaylov AF, Sonnenberg JL, Williams-Young D, Ding F, Lipparini F, Egidi F, Goings J, Peng B, Petrone A, Henderson T, Ranasinghe D, Zakrzewski VG, Gao J, Rega N, Zheng G, Liang W, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Throssell K, Montgomery JA Jr., Peralta JE, Ogliaro F, Bearpark MJ, Heyd JJ, Brothers EN, Kudin KN, Staroverov VN, Keith TA, Kobayashi R, Normand J, Raghavachari K, Rendell AP, Burant JC, Iyengar SS, Tomasi J, Cossi M, Millam JM, Klene M, Adamo C, Cammi R J. W. Ochterski, R. L. Martin, K. Morokuma, O. Farkas, J. B. Foresman, and D. J. Fox. Gaussian.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eLu T, Chen F, Multiwfn (2012) A multifunctional wavefunction analyzer. J Comput Chem 33:580\u0026ndash;592\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eWolinski K, Hinton JF, Pulay P (1990) Efficient implementation of the gauge-independent atomic orbital method for NMR chemical shift calculations. J Am Chem Soc 112:8251\u0026ndash;8260\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-7574907/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7574907/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eAtomic partial charges are local, model-dependent descriptors that often fail to capture the global electrostatic environment governing noncovalent interactions and reactivity. Here we show that the molecular electrostatic potential (ESP) at the Si\u0026ndash;H hydrogen in trisubstituted silanes is a decisive predictor of electrophilic versus nucleophilic behavior, whereas local charges alone are misleading. Using PBE0-D3/def2-TZVPP calculations, we evaluated atomic charges and ESP extrema in the gas phase and in two solvents, benzene and o-dichlorobenzene. Electron-donating groups (EDGs) generate hydridic hydrogens with a negative ESP near H (nucleophilic), while electron-withdrawing groups (EWGs) generally retain a negative local charge on H but induce a positive ESP region along the Si\u0026ndash;H axis (electrophilic). These effects are solvent dependent: with increasing dielectric constant, \u003cem\u003eV\u003c/em\u003e\u003csub\u003es,max\u003c/sub\u003e at H becomes more negative for EDG-substituted silanes and more positive for EWG-substituted silanes. The same solvent influence is mirrored in \u0026sup1;H NMR chemical shifts, producing upfield shifts for EDG- and downfield shifts for EWG-substituted silanes. Targeted experimental NMR measurements validate these predictions. The positive ESP region near H in EWG-substituted silanes is σ-hole-like in directionality, but unlike classical σ-holes arising from lone-pair depletion (e.g., halogens, chalcogens), it reflects a collective molecular ESP effect.\u003c/p\u003e","manuscriptTitle":"Ambiphilic Hydrogen in Trisubstituted Silanes: Substituent- Driven Polarity Flip Confirmed by NMR","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-09-29 06:12:18","doi":"10.21203/rs.3.rs-7574907/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"communications-chemistry","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"commschem","sideBox":"Learn more about [Communications Chemistry](http://www.nature.com/commschem/)","snPcode":"","submissionUrl":"","title":"Communications Chemistry","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Communications Series","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"8c9fad4c-68e7-495a-aa29-0d79ef221edb","owner":[],"postedDate":"September 29th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":55374572,"name":"Physical sciences/Chemistry/Theoretical chemistry/Computational chemistry"},{"id":55374573,"name":"Physical sciences/Chemistry/Analytical chemistry/NMR spectroscopy/Solution-state NMR"}],"tags":[],"updatedAt":"2026-05-13T07:07:58+00:00","versionOfRecord":{"articleIdentity":"rs-7574907","link":"https://doi.org/10.1038/s42004-026-01980-1","journal":{"identity":"communications-chemistry","isVorOnly":false,"title":"Communications Chemistry"},"publishedOn":"2026-03-20 04:00:00","publishedOnDateReadable":"March 20th, 2026"},"versionCreatedAt":"2025-09-29 06:12:18","video":"","vorDoi":"10.1038/s42004-026-01980-1","vorDoiUrl":"https://doi.org/10.1038/s42004-026-01980-1","workflowStages":[]},"version":"v1","identity":"rs-7574907","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7574907","identity":"rs-7574907","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}