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

doi:10.1039/b618806k

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

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

6 Citations (Scopus)

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 language	English
Pages (from-to)	2440-2449
Number of pages	10
Journal	Dalton Transactions
Issue number	23
DOIs	https://doi.org/10.1039/b618806k
Publication status	Published - Jun 13 2007

ASJC Scopus subject areas

Inorganic Chemistry

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Synthesis and structural studies of germyl and germyl/stannyl substituted tungstenocenes. / Khalimon, Andrey Yu; Dorogov, Konstantin Yu; Churakov, Andrei V.; Kuzmina, Lyudmila G.; Lemenovskii, Dmitry A.; Howard, Judith A.K.; Nikonov, Georgii I.

In: Dalton Transactions, No. 23, 13.06.2007, p. 2440-2449.

Research output: Contribution to journal › Article › peer-review

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title = "Synthesis and structural studies of germyl and germyl/stannyl substituted tungstenocenes",

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.",

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AU - Khalimon, Andrey Yu

AU - Dorogov, Konstantin Yu

AU - Churakov, Andrei V.

AU - Kuzmina, Lyudmila G.

AU - Lemenovskii, Dmitry A.

AU - Howard, Judith A.K.

AU - Nikonov, Georgii I.

PY - 2007/6/13

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N2 - 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.

AB - 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.

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