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

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

Access to Document

10.1039/b618806k

Fingerprint Dive into the research topics of 'Synthesis and structural studies of germyl and germyl/stannyl substituted tungstenocenes'. Together they form a unique fingerprint.

Cite this

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

@article{0c14c3aadfca49c99d30ed5e495a392d,

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.",

author = "Khalimon, {Andrey Yu} and Dorogov, {Konstantin Yu} and Churakov, {Andrei V.} and Kuzmina, {Lyudmila G.} and Lemenovskii, {Dmitry A.} and Howard, {Judith A.K.} and Nikonov, {Georgii I.}",

year = "2007",

month = jun,

day = "13",

doi = "10.1039/b618806k",

language = "English",

pages = "2440--2449",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "23",

}

TY - JOUR

T1 - Synthesis and structural studies of germyl and germyl/stannyl substituted tungstenocenes

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

Y1 - 2007/6/13

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.

UR - http://www.scopus.com/inward/record.url?scp=34250023169&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=34250023169&partnerID=8YFLogxK

U2 - 10.1039/b618806k

DO - 10.1039/b618806k

M3 - Article

AN - SCOPUS:34250023169

SP - 2440

EP - 2449

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 23

ER -