期刊
DALTON TRANSACTIONS
卷 42, 期 23, 页码 8276-8287出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c3dt50523e
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资金
- 'Liebig-Stipendium' of the 'Fonds der Chemischen Industrie'
A series of homologous potassium triphenylelement complexes [K(18-crown-6)EPh3] 6a-e of group 14 elements (E = C, Si, Ge, Sn, Pb) was synthesised by alkoxide induced heterolytic cleavage of boron-element compounds. The complexes 6a-e are isolated as storable solids possibly useful as sources of nucleophilic [EPh3](-) moieties. The solid state structures of 6a-e were established by X-ray crystal structure determination. Whilst all structures can be described as polymeric chains consisting of alternating [K(18-crown-6)](+) and [EPh3](-) units, the interaction within each chain varies systematically with the coordination properties of E. For Si and Ge, classical E-K coordination along with secondary phenyl-K interactions are characteristic, whilst for Sn and Pb, potassium coordination via the phenyl pi-system is observed due to inefficient coordination by the free electron pair localised in an 'inert' s-orbital. The carbon derivative is exceptional as the central sp(2)-hybridised carbon atom gives rise to extensive charge delocalisation and coordination via these partially charged pi-systems. A H-1-H-1 NOESY NMR spectroscopic study in THF-d(8) suggests appreciable anion/cation interactions for Si to Pb and hence the presence of contact ion pairs.
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