The use of bis(diphenylphosphinoacetylene) and its digold derivative as linking groups in osmium cluster chemistry. Crystal structures of [{Os3(CO)11}2(dppa)], [Os3,(CO)10(dppa)]2 and [Os4H(CO)12Au(dppa)]2 (dppa Ph2PCCPPh2)

Angelo J. Amoroso; Brian F.G. Johnson; Jack Lewis; Anju D. Massey; Paul R. Raithby; Wing Tak Wong

doi:10.1016/0022-328X(92)83498-7

The use of bis(diphenylphosphinoacetylene) and its digold derivative as linking groups in osmium cluster chemistry. Crystal structures of [{Os₃(CO)₁₁}₂(dppa)], [Os₃,(CO)₁₀(dppa)]₂ and [Os₄H(CO)₁₂Au(dppa)]₂ (dppa Ph₂PCCPPh₂)

Angelo J. Amoroso, Brian F.G. Johnson, Jack Lewis, Anju D. Massey, Paul R. Raithby, Wing Tak Wong

University of Cambridge

Research output: Contribution to journal › Article › peer-review

Abstract

The reaction of the activated triosmium cluster, [Os₃(CO)₁₁(NCMe)] with bis(diphenylphosphinoacetylene) (dppa) at room temperature affords the linked cluster [{Os₃(CO)_112}(dppa)] (1), while the reaction of [Os₃(CO)₁₀(NCMe)₂] with an excess of dppa affords the di-, tri- and tetrameric clusters [{Os₃(CO)₁₀(dppa)}₂] (2), [{Os₃(CO)₁₀(dppa)}₃] (3) and [{Os₃(CO)₁₀(dppa)}₄] (4) in moderate yields. Similarly, the reaction of the anion [Os₄H₃(CO)₁₂]^- with Au₂(dppa)Cl₂, in the presence of excess Et₃N and TIPF₆, under reflux, in chloroform affords [{Os₄H(CO)₁₂Audppa}₂] (5) as the only extractable product. Single crystal X-ray structural analyses of 1 and 2 show that the two triosmium cluster units are linked via coordination of one Os centre to each of the two phosphorus centres of the intact dppa ligand, while the structure of 5 shows the two tetraosmium units are linked via two μ₂-bridging Au centres and terminal phosphorus centres of the two Au(dppa) ligands.

Original language	English
Pages (from-to)	219-231
Number of pages	13
Journal	Journal of Organometallic Chemistry
Volume	440
Issue number	1-2
DOIs	https://doi.org/10.1016/0022-328X(92)83498-7
Publication status	Published - 17 Nov 1992

Funding

We thank the Nehru Trust of Cambridge University, Cambridge Commonwealth Trust (A.D.M.), the Royal Commission for the Exhibition of 1851 (W.T.W.), and the U.K. Committee of Vice Chancellors and Principals (W.T.W. & A.D.M.) and S.E.R.C. (A.J.A.) for financial support.

Funders	Funder number
Nehru Trust for Cambridge University
S.E.R.C.
Royal Commission for the Exhibition of 1851
Cambridge Commonwealth Trust

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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Amoroso, A. J., Johnson, B. F. G., Lewis, J., Massey, A. D., Raithby, P. R., & Wong, W. T. (1992). The use of bis(diphenylphosphinoacetylene) and its digold derivative as linking groups in osmium cluster chemistry. Crystal structures of [{Os₃(CO)₁₁}₂(dppa)], [Os₃,(CO)₁₀(dppa)]₂ and [Os₄H(CO)₁₂Au(dppa)]₂ (dppa Ph₂PCCPPh₂). Journal of Organometallic Chemistry, 440(1-2), 219-231. https://doi.org/10.1016/0022-328X(92)83498-7

The use of bis(diphenylphosphinoacetylene) and its digold derivative as linking groups in osmium cluster chemistry. Crystal structures of [{Os₃(CO)₁₁}₂(dppa)], [Os₃,(CO)₁₀(dppa)]₂ and [Os₄H(CO)₁₂Au(dppa)]₂ (dppa Ph₂PCCPPh₂). / Amoroso, Angelo J.; Johnson, Brian F.G.; Lewis, Jack et al.
In: Journal of Organometallic Chemistry, Vol. 440, No. 1-2, 17.11.1992, p. 219-231.

Research output: Contribution to journal › Article › peer-review

Amoroso, AJ, Johnson, BFG, Lewis, J, Massey, AD, Raithby, PR & Wong, WT 1992, 'The use of bis(diphenylphosphinoacetylene) and its digold derivative as linking groups in osmium cluster chemistry. Crystal structures of [{Os₃(CO)₁₁}₂(dppa)], [Os₃,(CO)₁₀(dppa)]₂ and [Os₄H(CO)₁₂Au(dppa)]₂ (dppa Ph₂PCCPPh₂)', Journal of Organometallic Chemistry, vol. 440, no. 1-2, pp. 219-231. https://doi.org/10.1016/0022-328X(92)83498-7

Amoroso AJ, Johnson BFG, Lewis J, Massey AD, Raithby PR, Wong WT. The use of bis(diphenylphosphinoacetylene) and its digold derivative as linking groups in osmium cluster chemistry. Crystal structures of [{Os₃(CO)₁₁}₂(dppa)], [Os₃,(CO)₁₀(dppa)]₂ and [Os₄H(CO)₁₂Au(dppa)]₂ (dppa Ph₂PCCPPh₂). Journal of Organometallic Chemistry. 1992 Nov 17;440(1-2):219-231. doi: 10.1016/0022-328X(92)83498-7

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abstract = "The reaction of the activated triosmium cluster, [Os3(CO)11(NCMe)] with bis(diphenylphosphinoacetylene) (dppa) at room temperature affords the linked cluster [{Os3(CO)112}(dppa)] (1), while the reaction of [Os3(CO)10(NCMe)2] with an excess of dppa affords the di-, tri- and tetrameric clusters [{Os3(CO)10(dppa)}2] (2), [{Os3(CO)10(dppa)}3] (3) and [{Os3(CO)10(dppa)}4] (4) in moderate yields. Similarly, the reaction of the anion [Os4H3(CO)12]- with Au2(dppa)Cl2, in the presence of excess Et3N and TIPF6, under reflux, in chloroform affords [{Os4H(CO)12Audppa}2] (5) as the only extractable product. Single crystal X-ray structural analyses of 1 and 2 show that the two triosmium cluster units are linked via coordination of one Os centre to each of the two phosphorus centres of the intact dppa ligand, while the structure of 5 shows the two tetraosmium units are linked via two μ2-bridging Au centres and terminal phosphorus centres of the two Au(dppa) ligands.",

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N2 - The reaction of the activated triosmium cluster, [Os3(CO)11(NCMe)] with bis(diphenylphosphinoacetylene) (dppa) at room temperature affords the linked cluster [{Os3(CO)112}(dppa)] (1), while the reaction of [Os3(CO)10(NCMe)2] with an excess of dppa affords the di-, tri- and tetrameric clusters [{Os3(CO)10(dppa)}2] (2), [{Os3(CO)10(dppa)}3] (3) and [{Os3(CO)10(dppa)}4] (4) in moderate yields. Similarly, the reaction of the anion [Os4H3(CO)12]- with Au2(dppa)Cl2, in the presence of excess Et3N and TIPF6, under reflux, in chloroform affords [{Os4H(CO)12Audppa}2] (5) as the only extractable product. Single crystal X-ray structural analyses of 1 and 2 show that the two triosmium cluster units are linked via coordination of one Os centre to each of the two phosphorus centres of the intact dppa ligand, while the structure of 5 shows the two tetraosmium units are linked via two μ2-bridging Au centres and terminal phosphorus centres of the two Au(dppa) ligands.

AB - The reaction of the activated triosmium cluster, [Os3(CO)11(NCMe)] with bis(diphenylphosphinoacetylene) (dppa) at room temperature affords the linked cluster [{Os3(CO)112}(dppa)] (1), while the reaction of [Os3(CO)10(NCMe)2] with an excess of dppa affords the di-, tri- and tetrameric clusters [{Os3(CO)10(dppa)}2] (2), [{Os3(CO)10(dppa)}3] (3) and [{Os3(CO)10(dppa)}4] (4) in moderate yields. Similarly, the reaction of the anion [Os4H3(CO)12]- with Au2(dppa)Cl2, in the presence of excess Et3N and TIPF6, under reflux, in chloroform affords [{Os4H(CO)12Audppa}2] (5) as the only extractable product. Single crystal X-ray structural analyses of 1 and 2 show that the two triosmium cluster units are linked via coordination of one Os centre to each of the two phosphorus centres of the intact dppa ligand, while the structure of 5 shows the two tetraosmium units are linked via two μ2-bridging Au centres and terminal phosphorus centres of the two Au(dppa) ligands.

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