The title compounds exhibit an imperfect C3 geometry: in addition to the four sigma-bonds (Si-H or Si-F and three Si-C), three weak donating Si<--N interactions ranging from 2.87 to 3.47(1) angstrom are also observed. The overall tetrahedral environment of the silicon (or germanium) atom is retained, and the structure can be described as a ''tricapped tetrahedron''. In most cases, and despite the large distances encountered, the nitrogen lone pair is directed toward the silicon atom opposite to an aryl-silicon bond. In the case of the fluorosilane no dative bonding opposite to the fluorine atom is observed, and the approach of the three amino groups occurs exclusively on the frontal faces of the Si-F bond. Steric hindrance appears as the critical factor preventing closer approach of the three nitrogen lone pairs to the silicon atom.

AbstractThe oxidation of the five‐coordinate silane (I) using CS2, S8, or Sex results in the formation of the silanethione (IVa) or silaneselenone (IVb), respectively.

Silanethione 2a and silaneselenone 2b—stabilized by intramolecular Si ← N coordination— are obtained as shown below. The X-ray structure analysis of 2a, 1-naphthyl instead of phenyl, reveals strong zwitterionic character, which might explain the unexpectedly low reactivity toward nucleophiles and electrophiles (a, X = S; b, X = Se).

Silanthione 2a und Silanselone 2b ‐ durch intramolekulare Si←N‐Koordination stabilisiert ‐ sind wie unten angegeben erhalten worden. Bei 2a, 1‐Naphthyl statt Phenyl, weist die Röntgenstrukturanalyse auf einen starken zwitterionischen Charakter hin, der die unerwartet geringe Reaktivität gegenüber Nucleophilen und Elektrophilen erklären könnte (a, X = S; b, X = Se).magnified image

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPush-pull intermolecular nucleophile-electrophile interactions of carbonyl groups from crystallographic data and MNDO calculationsMichele Cossu, Christian Bachmann, Thomas Yao N'Guessan, Robert Viani, Jacques Lapasset, Jean Pierre Aycard, and Hubert BodotCite this: J. Org. Chem. 1987, 52, 24, 5313–5319Publication Date (Print):November 1, 1987Publication History Published online1 May 2002Published inissue 1 November 1987https://pubs.acs.org/doi/10.1021/jo00233a003https://doi.org/10.1021/jo00233a003research-articleACS PublicationsRequest reuse permissionsArticle Views64Altmetric-Citations8LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-AlertscloseSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTIntramolecular interactions. 33. Conformational and geometrical adaptations to strong gauche interactions: analysis of the x-ray crystallographic data of six congested 3-tert-butylcyclohexene derivativesRobert Viani, Jacques Lapasset, Jean Pierre Aycard, and Hubert BodotCite this: J. Org. Chem. 1979, 44, 6, 899–902Publication Date (Print):March 1, 1979Publication History Published online1 May 2002Published inissue 1 March 1979https://pubs.acs.org/doi/10.1021/jo01320a001https://doi.org/10.1021/jo01320a001research-articleACS PublicationsRequest reuse permissionsArticle Views45Altmetric-Citations6LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts