Synthesis and structural studies of germyl and germyl/stannyl substituted tungstenocenes

Andrey Yu Khalimon, Konstantin Yu Dorogov, Andrei V. Churakov, Lyudmila G. Kuzmina, Dmitry A. Lemenovskii, Judith A.K. Howard, Georgii I. Nikonov

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Abstract

One-pot reactions of [WCp2(H)2] and [WCp 2(H)(SnMe3)] with nBuLi followed by an equivalent of GeMe2Cl2 afford mono(germyl) substituted tungstenocenes [WCp2(H)(GeMe2Cl)] (1) and [WCp 2(SnMe3)(GeMe2Cl)] (7). Reactions of the products with tin halides in the presence NEt3 afford the mixed complexes [WCp2(SnR2X)(GeMe2Y)] (X, Y = Cl, Br, RMe, Et), which were further converted to moderately stable compounds [WCp 2(SnR2H)(GeMe2H)] (R = Me (10), Et (11)). A number of asymmetric mono(halo)-substituted germyl/stannyl tungstenocenes [WCp2(SnMe2X)(GeMe2H)] (X = Cl (12), Br (13)) and [WCp2(SnEt2Y)(GeMe2H)] (Y = Br (14), I (15)) were prepared by selective halogenation of the Sn-H bond in 10 and 11. X-Ray studies of [WCp2(H)(GeMe2Cl)] (1), [WCp 2(SnEt2Br)(GeMe2Cl)] (4), and [WCp 2(SnEt2Br)(GeMe2H)] (14) established classical structures of these compounds. X-Ray study of complex [WCp2(SnMe 2Cl)(GeMe2Cl)] (3) revealed the presence of interligand Ge-Cl⋯Sn-Cl interactions in a highly Ge/Sn disordered structure. Analyses of molecular parameters of 1, 4, and 14 suggest the presence of a negative hyperconjugation between metal lone pairs and the σ*-orbital of the E-X bond, which is stronger in bromo substituted complexes in comparison with chloro substituted ones.

Original languageEnglish
Pages (from-to)2440-2449
Number of pages10
JournalDalton Transactions
Issue number23
DOIs
Publication statusPublished - Jun 13 2007

ASJC Scopus subject areas

  • Inorganic Chemistry

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    Khalimon, A. Y., Dorogov, K. Y., Churakov, A. V., Kuzmina, L. G., Lemenovskii, D. A., Howard, J. A. K., & Nikonov, G. I. (2007). Synthesis and structural studies of germyl and germyl/stannyl substituted tungstenocenes. Dalton Transactions, (23), 2440-2449. https://doi.org/10.1039/b618806k