Trans-cis octahedral interconversion pathway in diorganotin compounds |
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Authors: | Miriam Rossi |
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Institution: | a Vassar College, Department of Chemistry, Poughkeepsie NY 12604-0484, USA b Istituto di Chimica Biomolecolare, Consiglio Nazionale delle Ricerche (CNR), Piazzale Aldo Moro 5, 00185 Rome, Italy |
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Abstract: | Using structural data from bis(bidentate)diorganotin compounds in the Cambridge Structural Database a potential pathway for trans-cis interconversion is envisaged with nondissociative Sn-donor bonds and retaining metal coordination number 6. C-Sn-C bond angles in the range 180-145° correspond to skewed trapezoid bipyramidal geometry for 6- and 5-membered O,O′ chelates; geometries that resemble the transition state of the trans-cis pathway starts forming at about C-Sn-C 134°. cis-Diorganotins explored in this work have C-Sn-C bond angles in the range 102-110°; it is the statistically favored configuration for diphenyltins. The proposed trans-cis conversion pathway is deduced from a series of geometries associated with decreasing the C-Sn-C bond angle and shows 2 weakly (secondary) bound chelating atoms lengthening their bonds until near the transition state and later strengthening; they end up cis to each other and opposite to the organic groups. Conversely, the other 2 (primary) donors shorten their bonds until the transition state is reached and later lengthen; they end up trans to each other. The entire transformation from trans to cis configuration occurs with relative rotation of 3 bonds. |
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Keywords: | Diorganotin Cis-trans Conversion Bidentate Octahedron |
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