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

Preparation and coordinating properties of {CH2(o-C6H4CH2SbMe2)}(2), a novel wide-angle cis-chelating distibine
Preparation and coordinating properties of {CH2(o-C6H4CH2SbMe2)}(2), a novel wide-angle cis-chelating distibine
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)].
ray crystal-structure, complexes, ligands, chemistry, platinum(ii), derivatives, tungsten, stibine, xylyl, route
1477-9226
5648-5654
Brown, Michael D.
76a42341-1a1e-4ec9-8cdc-aca9d5e53bf4
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7
Brown, Michael D.
76a42341-1a1e-4ec9-8cdc-aca9d5e53bf4
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7

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).

Record type: Article

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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Published date: 2006
Keywords: ray crystal-structure, complexes, ligands, chemistry, platinum(ii), derivatives, tungsten, stibine, xylyl, route

Identifiers

Local EPrints ID: 44574
URI: http://eprints.soton.ac.uk/id/eprint/44574
ISSN: 1477-9226
PURE UUID: b2749f0c-da3a-4e76-a0ac-3c34dfdcf8f2
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 01 Mar 2007
Last modified: 10 Sep 2019 00:57

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Contributors

Author: Michael D. Brown
Author: William Levason ORCID iD
Author: Gillian Reid ORCID iD
Author: Michael Webster

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