The reduction of triosmium dodecacarbonyl by sodium borohydride. The preparation and X-ray structure of the cluster anion [H2Os4(CO)12]2-

Brian F.G. Johnson; Jack Lewis; Paul R. Raithby; George M. Sheldrick; Georg Süss

doi:10.1016/S0022-328X(00)82036-7

The reduction of triosmium dodecacarbonyl by sodium borohydride. The preparation and X-ray structure of the cluster anion [H₂Os₄(CO)₁₂]^2-

Brian F.G. Johnson, Jack Lewis, Paul R. Raithby, George M. Sheldrick, Georg Süss

University of Cambridge

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

Abstract

The reduction of Os₃(CO)₁₂ by NaBH₄ in tetrahydrofuran has been studied, and the formation of the anionic clusters [HOs₃(CO)₁₁]^-, [H₃Os₄(CO)₁₂]^- and [H₂Os₄(CO)₁₂]^2- observed. The previously unreported dianion [H₂Os₄(CO)₁₂]^2- was prepared in satisfactory yield, and characterised as the bis(triphenylphosphine)iminium salt. This compound crystallizes in the space group P1, with Z = 1, and cell dimensions of a 11.014(2), b 14.751(3), c 15.168(3) Å, α 123.95(2)°, β 95.77(2)°, γ 98.73(2)°. The structure was solved by a combination of multisolution sign expansion and Fourier methods, and final residuals were R 0.067 and R_W 0.066 for 5972 observed intensity data. The dianion comprises a distorted tetrahedron of osmium atoms, each metal also bonding to three terminal carbonyl ligands, which as staggered with respect to the metalmetal bonds. Unlike the cation, the cluster anion is statistically disordered between two centrosymmetrically related sites.

Original language	English
Pages (from-to)	179-187
Number of pages	9
Journal	Journal of Organometallic Chemistry
Volume	162
Issue number	2
DOIs	https://doi.org/10.1016/S0022-328X(00)82036-7
Publication status	Published - 12 Dec 1978

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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@article{2316136fd61649f6b7d07d48eb5d2ec7,

title = "The reduction of triosmium dodecacarbonyl by sodium borohydride. The preparation and X-ray structure of the cluster anion [H2Os4(CO)12]2-",

abstract = "The reduction of Os3(CO)12 by NaBH4 in tetrahydrofuran has been studied, and the formation of the anionic clusters [HOs3(CO)11]-, [H3Os4(CO)12]- and [H2Os4(CO)12]2- observed. The previously unreported dianion [H2Os4(CO)12]2- was prepared in satisfactory yield, and characterised as the bis(triphenylphosphine)iminium salt. This compound crystallizes in the space group P1, with Z = 1, and cell dimensions of a 11.014(2), b 14.751(3), c 15.168(3) {\AA}, α 123.95(2)°, β 95.77(2)°, γ 98.73(2)°. The structure was solved by a combination of multisolution sign expansion and Fourier methods, and final residuals were R 0.067 and RW 0.066 for 5972 observed intensity data. The dianion comprises a distorted tetrahedron of osmium atoms, each metal also bonding to three terminal carbonyl ligands, which as staggered with respect to the metalmetal bonds. Unlike the cation, the cluster anion is statistically disordered between two centrosymmetrically related sites.",

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doi = "10.1016/S0022-328X(00)82036-7",

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AU - Johnson, Brian F.G.

AU - Lewis, Jack

AU - Raithby, Paul R.

AU - Sheldrick, George M.

AU - Süss, Georg

PY - 1978/12/12

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N2 - The reduction of Os3(CO)12 by NaBH4 in tetrahydrofuran has been studied, and the formation of the anionic clusters [HOs3(CO)11]-, [H3Os4(CO)12]- and [H2Os4(CO)12]2- observed. The previously unreported dianion [H2Os4(CO)12]2- was prepared in satisfactory yield, and characterised as the bis(triphenylphosphine)iminium salt. This compound crystallizes in the space group P1, with Z = 1, and cell dimensions of a 11.014(2), b 14.751(3), c 15.168(3) Å, α 123.95(2)°, β 95.77(2)°, γ 98.73(2)°. The structure was solved by a combination of multisolution sign expansion and Fourier methods, and final residuals were R 0.067 and RW 0.066 for 5972 observed intensity data. The dianion comprises a distorted tetrahedron of osmium atoms, each metal also bonding to three terminal carbonyl ligands, which as staggered with respect to the metalmetal bonds. Unlike the cation, the cluster anion is statistically disordered between two centrosymmetrically related sites.

AB - The reduction of Os3(CO)12 by NaBH4 in tetrahydrofuran has been studied, and the formation of the anionic clusters [HOs3(CO)11]-, [H3Os4(CO)12]- and [H2Os4(CO)12]2- observed. The previously unreported dianion [H2Os4(CO)12]2- was prepared in satisfactory yield, and characterised as the bis(triphenylphosphine)iminium salt. This compound crystallizes in the space group P1, with Z = 1, and cell dimensions of a 11.014(2), b 14.751(3), c 15.168(3) Å, α 123.95(2)°, β 95.77(2)°, γ 98.73(2)°. The structure was solved by a combination of multisolution sign expansion and Fourier methods, and final residuals were R 0.067 and RW 0.066 for 5972 observed intensity data. The dianion comprises a distorted tetrahedron of osmium atoms, each metal also bonding to three terminal carbonyl ligands, which as staggered with respect to the metalmetal bonds. Unlike the cation, the cluster anion is statistically disordered between two centrosymmetrically related sites.

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The reduction of triosmium dodecacarbonyl by sodium borohydride. The preparation and X-ray structure of the cluster anion [H₂Os₄(CO)₁₂]^2-

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