Preparation and coordinating properties of {CH2(o-C6H4CH2SbMe2)}(2), a novel wide-angle cis-chelating distibine

Brown, Michael D., Levason, William, Reid, Gillian and Webster, Michael (2006) Preparation and coordinating properties of {CH2(o-C6H4CH2SbMe2)}(2), a novel wide-angle cis-chelating distibine. Dalton Transactions, (47), 5648-5654. (doi:10.1039/b610808c).

Abstract

The unique wide-angle distibine, {CH2(o-C6H4CH2SbMe2)}(2), 1, has been prepared indirectly by reaction of Me2SbCl with the di-Grignard formed unexpectedly by coupling of o-C6H4(CH2MgCl)(2) in concentrated thf solution, and directly by treatment of the {CH2(o-C6H4CH2MgCl)}(2) with Me2SbCl. The very oxygen-sensitive distibine 1 has been characterised by H-1 and C-13{H-1} NMR spectroscopy and high-resolution EIMS. Oxidation of 1 with Br-2 gives the air-stable tetrabromide {CH2(o-C6H4CH2SbMe2Br2)}(2). Surprisingly, 1 shows a very strong tendency to function as a cis-chelate, e.g. to Pt(IV) in the complex [PtMe3I(1)], forming an 11-membered ring and providing a stable Pt(IV) stibine complex, the crystal structure of which shows the Sb-Pt-Sb angle to be 95.96(1)degrees. The yellow Pt(II) complex [PtCl2(1)] is obtained from reaction of [PtCl2(MeCN)(2)] with 1 and IR spectroscopic data and a crystal structure determination confirm the Cl ligands are mutually cis in this species. Reaction of [W(CO)(4)(piperidine)(2)] with 1 in refluxing EtOH gives [W(CO)(4)(1)], the IR spectrum of which shows four v(CO) bands, also consistent with cis-Sb-2 coordination. The cis-chelation is also confirmed by single-crystal X-ray structure determinations of two polymorphs of [W(CO)(4)(1)].

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Contributors

Author: William Levason

Author: Gillian Reid

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