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Vibrational, P-31 NMR and crystallographic studies of diiodine adducts of some bidentate tertiary phosphine sulfides

Vibrational, P-31 NMR and crystallographic studies of diiodine adducts of some bidentate tertiary phosphine sulfides
Vibrational, P-31 NMR and crystallographic studies of diiodine adducts of some bidentate tertiary phosphine sulfides
Treatment of bis(dipbenylphosphino)methane disulfide (dppmS) or bis(diphenylphosphino)ethane disulfide (dppeS) with diiodine in dichloromethane yields the adducts dppmS .I-4 1 and dppeS .I-4 2, respectively, whose structures have been solved by X-ray crystallography. Compounds 1 and 2 consist of discrete molecular units containing bent P-S-I and linear S . . .I-I geometries that can be interpreted in terms of donation of electron density from sulfur to diiodine. Consistent with this interpretation, the P-S bonds are lengthened compared to the unco-ordinated phosphine sulfides, and the I-I bonds are lengthened compared to unco-ordinated diiodine. Both compounds can therefore be described as 'charge-transfer' complexes. The two S . . .I-I moieties in 1 are inequivalent having markedly different bond lengths and angles. In 2 both S . . .I-I moieties are identical. The structural features of 1 and 2 are in accordance with Raman and P-31 CP MAS NMR data.
tertiary phosphine sulfide, bis(diphenylphosphino)methane disulfide, bis(diphenylphosphino)ethane disulfide, diiodine, charge-transfer complexes
0277-5387
1907-1913
Apperley, David C.
b2426389-4481-4047-90d3-ac56c434111b
Bricklebank, Neil
6e082c98-a747-4690-bb37-f05f24d621f5
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Apperley, David C.
b2426389-4481-4047-90d3-ac56c434111b
Bricklebank, Neil
6e082c98-a747-4690-bb37-f05f24d621f5
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8

Apperley, David C., Bricklebank, Neil, Hursthouse, Michael B., Light, Mark E. and Coles, Simon J. (2001) Vibrational, P-31 NMR and crystallographic studies of diiodine adducts of some bidentate tertiary phosphine sulfides. Polyhedron, 20 (15-16), 1907-1913. (doi:10.1016/S0277-5387(01)00773-2).

Record type: Article

Abstract

Treatment of bis(dipbenylphosphino)methane disulfide (dppmS) or bis(diphenylphosphino)ethane disulfide (dppeS) with diiodine in dichloromethane yields the adducts dppmS .I-4 1 and dppeS .I-4 2, respectively, whose structures have been solved by X-ray crystallography. Compounds 1 and 2 consist of discrete molecular units containing bent P-S-I and linear S . . .I-I geometries that can be interpreted in terms of donation of electron density from sulfur to diiodine. Consistent with this interpretation, the P-S bonds are lengthened compared to the unco-ordinated phosphine sulfides, and the I-I bonds are lengthened compared to unco-ordinated diiodine. Both compounds can therefore be described as 'charge-transfer' complexes. The two S . . .I-I moieties in 1 are inequivalent having markedly different bond lengths and angles. In 2 both S . . .I-I moieties are identical. The structural features of 1 and 2 are in accordance with Raman and P-31 CP MAS NMR data.

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More information

Published date: 2001
Keywords: tertiary phosphine sulfide, bis(diphenylphosphino)methane disulfide, bis(diphenylphosphino)ethane disulfide, diiodine, charge-transfer complexes

Identifiers

Local EPrints ID: 39124
URI: https://eprints.soton.ac.uk/id/eprint/39124
ISSN: 0277-5387
PURE UUID: 677074d7-7cc0-4820-a253-e2e59c896afd
ORCID for Mark E. Light: ORCID iD orcid.org/0000-0002-0585-0843
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

Catalogue record

Date deposited: 21 Jun 2006
Last modified: 20 Jul 2019 01:10

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