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Reactivity of the unsaturated triosmium cluster [Os3(CO)8{Ph2PCH2P(Ph)C6H4}(mu-H)] with thiols

Reactivity of the unsaturated triosmium cluster [Os3(CO)8{Ph2PCH2P(Ph)C6H4}(mu-H)] with thiols
Reactivity of the unsaturated triosmium cluster [Os3(CO)8{Ph2PCH2P(Ph)C6H4}(mu-H)] with thiols
The reaction of the unsaturated cluster [(mu -H)Os-3(CO)(8) {Ph2PCH2P(Ph)C6H4}] 2 with C2H5SH, CH3CH(CH3)SH and C6H5SH are reported. The reaction of 2 with C2H5SH yields the new complexes [Os-3(CO)(8)(mu -SC2H5)(eta (1)-SC2H5) {Ph2PCH2P(Ph)C6H4}(mu -H)] 9 and [Os-3(CO)(8))( SC2H5)(Ph2PCH2P)(Ph) C6H4}] 8 in 24 and 57% yields respectively and the known compound [(Os-3(CO)(8))(mu -SC2H5)(mu -dppm)(mu -H)] 7 in 5% yield. Compound 9, which exists as two isomers in solution, converts into 8 almost quantitatively in solution at 25 degreesC and more rapidly in refluxing hexane. Compound 8 reacts with H-2, at 110 degreesC to give 7 in high yield (86%). Treatment of 2 with propane-2-thiol yields [Os-3(CO)(8){mu -SCH(CH3)CH3} {Ph2PCH2P(Ph)C6H4}] 10 and [(Os-3 (CO)(8){mu -SCH(CH3)CH3} {eta (1)-SCN(CH3)CH3} {Ph2PCH2P(Ph)C6H4} (mu -H)] 11 in 75 and 3% yields respectively while with C6H5SH, [(Os-3(CO)(8)(mu- SC6H5)(mu -dppm)(mu -H)] 6 is obtained as the only product in 75 % yield. In both 8 and 10, the thiolato ligand bridges the Os-Os edge which is also bridged by the metallated phenyl group. The neu compounds have been characterized by elemental analyses and spectroscopic methods (IR, H-1 and P-31 NMR). The molecular structures of 7, 8, 9 and 10 are reported as determined by X-ray diffraction studies.
osmium cluster, reaction with thiols, ray crystal-structures, carbon-disulfide, complexes, ligands, sulfur, desulfurization, hydrogenation, coordination, h2os3(co)10, ph2pch2pph2
1040-7278
5-22
Abedin, S.M. Tareque
31fc449f-ec1c-43a2-8132-9cb7c59e6b59
Azam, Kazi A.
dbe11988-64ef-4d83-ba75-8788aac9d499
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Kabir, Shariff E.
15de2739-09d6-475b-abaf-700fa99f4540
Malik, K.M. Abdul
8e80df0d-327c-4dd1-b42b-15600c152a46
Mottalib, Md. Abdul
55b493ad-e833-494d-871a-d23d406e12ad
Rosenberg, Edward
6b2026bb-f048-4511-baa7-671c4b9382f2
Abedin, S.M. Tareque
31fc449f-ec1c-43a2-8132-9cb7c59e6b59
Azam, Kazi A.
dbe11988-64ef-4d83-ba75-8788aac9d499
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Kabir, Shariff E.
15de2739-09d6-475b-abaf-700fa99f4540
Malik, K.M. Abdul
8e80df0d-327c-4dd1-b42b-15600c152a46
Mottalib, Md. Abdul
55b493ad-e833-494d-871a-d23d406e12ad
Rosenberg, Edward
6b2026bb-f048-4511-baa7-671c4b9382f2

Abedin, S.M. Tareque, Azam, Kazi A., Hursthouse, Michael B., Kabir, Shariff E., Malik, K.M. Abdul, Mottalib, Md. Abdul and Rosenberg, Edward (2001) Reactivity of the unsaturated triosmium cluster [Os3(CO)8{Ph2PCH2P(Ph)C6H4}(mu-H)] with thiols. Journal of Cluster Science, 12 (1), 5-22. (doi:10.1023/A:1016606609077).

Record type: Article

Abstract

The reaction of the unsaturated cluster [(mu -H)Os-3(CO)(8) {Ph2PCH2P(Ph)C6H4}] 2 with C2H5SH, CH3CH(CH3)SH and C6H5SH are reported. The reaction of 2 with C2H5SH yields the new complexes [Os-3(CO)(8)(mu -SC2H5)(eta (1)-SC2H5) {Ph2PCH2P(Ph)C6H4}(mu -H)] 9 and [Os-3(CO)(8))( SC2H5)(Ph2PCH2P)(Ph) C6H4}] 8 in 24 and 57% yields respectively and the known compound [(Os-3(CO)(8))(mu -SC2H5)(mu -dppm)(mu -H)] 7 in 5% yield. Compound 9, which exists as two isomers in solution, converts into 8 almost quantitatively in solution at 25 degreesC and more rapidly in refluxing hexane. Compound 8 reacts with H-2, at 110 degreesC to give 7 in high yield (86%). Treatment of 2 with propane-2-thiol yields [Os-3(CO)(8){mu -SCH(CH3)CH3} {Ph2PCH2P(Ph)C6H4}] 10 and [(Os-3 (CO)(8){mu -SCH(CH3)CH3} {eta (1)-SCN(CH3)CH3} {Ph2PCH2P(Ph)C6H4} (mu -H)] 11 in 75 and 3% yields respectively while with C6H5SH, [(Os-3(CO)(8)(mu- SC6H5)(mu -dppm)(mu -H)] 6 is obtained as the only product in 75 % yield. In both 8 and 10, the thiolato ligand bridges the Os-Os edge which is also bridged by the metallated phenyl group. The neu compounds have been characterized by elemental analyses and spectroscopic methods (IR, H-1 and P-31 NMR). The molecular structures of 7, 8, 9 and 10 are reported as determined by X-ray diffraction studies.

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More information

Published date: 2001
Keywords: osmium cluster, reaction with thiols, ray crystal-structures, carbon-disulfide, complexes, ligands, sulfur, desulfurization, hydrogenation, coordination, h2os3(co)10, ph2pch2pph2

Identifiers

Local EPrints ID: 19372
URI: https://eprints.soton.ac.uk/id/eprint/19372
ISSN: 1040-7278
PURE UUID: 0acb8606-d3c8-401d-b155-d481ccf42010

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Date deposited: 13 Feb 2006
Last modified: 17 Jul 2017 16:31

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