TY - JOUR
T1 - Products of the pyrolysis of [Os3(CO)11{P(OMe)3}]; The molecular and crystal structure of [Os5C(CO)13H{OP(OMe)2}{P(OMe)3}]
AU - Fernandez, Juan M.
AU - Johnson, Brian F.G.
AU - Lewis, Jack
AU - Raithby, Paul R.
PY - 1981
Y1 - 1981
N2 - The pyrolysis of [Os3(CO)11{P(OMe)3}] leads to the formation of four cluster carbonyl complexes containing five Os atoms which have been characterised as [Os5C(CO)14H{OP(OMe)2}] (3), [Os5C(CO)13H{OP(OMe)2}{P(OMe)3}] (7a), [Os5C(CO)13H{OP(OMe)OP(OMe)2}] (5), and [Os5(CO)15{P(OMe)}] (2) by spectroscopic and X-ray single-crystal analyses. The full crystal structure of (7a) is reported; the complex crystallises in the triclinic space group P1, with a = 11.623(2), b = 15.937(2), c = 18.515(4) Å, α = 104.01(2), β = 98.85(2), γ = 91.65(1)°, and Z = 4. The structure has been solved by a combination of multisolution Σ2 sign expansion and Fourier-difference techniques, and refined by blocked full-matrix least squares to R = 0.054 for 8 446 unique observed diffractometer data. The nature and mode of co-ordination of the ligands derived from the phosphite group varies from complex to complex, and there is a stepwise progression for the first three compounds in which replacement of a carbonyl group is followed by an eventual linking of two phosphite ligands on the cluster surface. The structures of the four complexes are discussed briefly in terms of the number of electrons present.
AB - The pyrolysis of [Os3(CO)11{P(OMe)3}] leads to the formation of four cluster carbonyl complexes containing five Os atoms which have been characterised as [Os5C(CO)14H{OP(OMe)2}] (3), [Os5C(CO)13H{OP(OMe)2}{P(OMe)3}] (7a), [Os5C(CO)13H{OP(OMe)OP(OMe)2}] (5), and [Os5(CO)15{P(OMe)}] (2) by spectroscopic and X-ray single-crystal analyses. The full crystal structure of (7a) is reported; the complex crystallises in the triclinic space group P1, with a = 11.623(2), b = 15.937(2), c = 18.515(4) Å, α = 104.01(2), β = 98.85(2), γ = 91.65(1)°, and Z = 4. The structure has been solved by a combination of multisolution Σ2 sign expansion and Fourier-difference techniques, and refined by blocked full-matrix least squares to R = 0.054 for 8 446 unique observed diffractometer data. The nature and mode of co-ordination of the ligands derived from the phosphite group varies from complex to complex, and there is a stepwise progression for the first three compounds in which replacement of a carbonyl group is followed by an eventual linking of two phosphite ligands on the cluster surface. The structures of the four complexes are discussed briefly in terms of the number of electrons present.
UR - https://www.scopus.com/pages/publications/37049095290
U2 - 10.1039/DT9810002250
DO - 10.1039/DT9810002250
M3 - Article
AN - SCOPUS:37049095290
SN - 1472-7773
SP - 2250
EP - 2257
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 11
ER -