Crystalline Silagermenides: Unraveling π-Bonding and Lone Pair Effects in the Multiple Bonds of Heavier Vinyl Anion Analogs

Crystalline Silagermenides: Unraveling π-Bonding and Lone Pair Effects in the Multiple Bonds of Heavier Vinyl Anion Analogs | 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 Research Article Crystalline Silagermenides: Unraveling π-Bonding and Lone Pair Effects in the Multiple Bonds of Heavier Vinyl Anion Analogs Xue-Yi He, Qiuming Liang, Yanbo Mei, Liu Leo Liu This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6166457/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 06 Apr, 2025 Read the published version in Angewandte Chemie International Edition → Version 1 posted You are reading this latest preprint version Abstract Compared to vinyl anions, their heavier heteronuclear analogs silagermenides in the form of [R 2 Si═GeR]ˉ remain exceedingly rare. Herein, we present a systematic investigation of silagermenides, synthesized via a straightforward desilylation route. We delve into the bonding characteristics, revealing a weak, polarized Si–Ge π bond with a significant nonbonded lone pair character at the β-Si position. This β-Si exhibits predominantly nucleophilic behavior, while the α-Ge position demonstrates subtly electrophilic tendencies, despite the presence of a vinylic, formally anionic Ge atom. This behavior leads to the formation of silagermenide complexes in an unprecedented η 2 coordination mode, as well as various silagermenes and a germylene with unconventional substituents. Cleavage of the Si═Ge double bond was also revealed. Our findings expand the understanding of heavier vinyl anion analogs, with important implications for their synthesis and reactivity. Inorganic Chemistry Silagermenide Desilylation Silagermene Polarized π Bond Gold Complexes Full Text Additional Declarations The authors declare no competing interests. Supplementary Files SIpreprint.pdf Cite Share Download PDF Status: Published Journal Publication published 06 Apr, 2025 Read the published version in Angewandte Chemie International Edition → 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. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-6166457","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":424813621,"identity":"e21aee77-1ed5-4da4-8d13-fe923a4301c4","order_by":0,"name":"Xue-Yi He","email":"","orcid":"","institution":"SUSTech","correspondingAuthor":false,"prefix":"","firstName":"Xue-Yi","middleName":"","lastName":"He","suffix":""},{"id":424813622,"identity":"27faae48-4d36-4fcb-b1b9-2264caefd531","order_by":1,"name":"Qiuming Liang","email":"","orcid":"","institution":"Great Bay 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Herein, we present a systematic investigation of silagermenides, synthesized via a straightforward desilylation route. We delve into the bonding characteristics, revealing a weak, polarized Si–Ge π bond with a significant nonbonded lone pair character at the β-Si position. This β-Si exhibits predominantly nucleophilic behavior, while the α-Ge position demonstrates subtly electrophilic tendencies, despite the presence of a vinylic, formally anionic Ge atom. This behavior leads to the formation of silagermenide complexes in an unprecedented \u003cem\u003eη\u003c/em\u003e\u003csup\u003e2\u003c/sup\u003e coordination mode, as well as various silagermenes and a germylene with unconventional substituents. Cleavage of the Si═Ge double bond was also revealed. 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