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Synthesis and Reactions of Tungsten(II) Norbornandiene (nbd) Complexes. The Crystal and Molecular Structure of

DOI: 10.1039/DT9930003341

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Journal of the Chemical Society, Dalton Transactions p. 3341 - 3348 (1993)

Update date:2022-08-02

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Authors:

Carlton, LaurenceCarlton, Laurence

Davidson, Jack L.Davidson, Jack L.

Vasapollo, GiuseppeVasapollo, Giuseppe

Douglas, GraemeDouglas, Graeme

Muir, Kenneth W.Muir, Kenneth W.

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Article abstract of DOI:10.1039/DT9930003341

The reaction of 1 (nbd = norbornandiene) with Tl(C5H5) gave a monocarbonyl derivative 5-C5H5)> 2.With Tl(O2CMe) and Tl, complex 1 gave monosubstituted derivatives 3a and (CO)2(nbd)> 3b which appear to be seven-co-ordinate according to IR data.In contrast 1 and Tl(SC6F5) (1:1 molar ratio) gave the six-co-ordinate complex 4.An X-ray diffraction study of 4 established that it has a distorted-octahedral structure with trans W-CO bonds approximately perpendicular to a plane containing the W, Br and S atoms and the midpoints of the nbd C=C bonds.Simple electronic arguments provide a rationalisation of many of the structural features of 4.Reaction of 1 with 2 molar equivalents of Tl(SC6F5) gave the bis(thiolate) derivative 5 again with a trans arrangement of CO ligands.The reactions of 5 with L = PEt3, PMe2Ph or P(OMe)3 gave the six-co-ordinate complexes 6 which exist in two isomeric forms, red or green.Dynamic NMR studies have been used to characterise the isomeric behaviour and fluxional processes in the complexes.

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Product name:WBr(SC6F5)(CO)2(norbornadiene)

Cas No:153980-25-7

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