Nonacarbonyldinitrosyltriosmium: its synthesis and reactivity

Bhaduri, Sumit ; Johnson, Brian F. G. ; Lewis, Jack ; Watson, Douglas J. ; Zuccaro, Camillo (1979) Nonacarbonyldinitrosyltriosmium: its synthesis and reactivity Journal of the Chemical Society Dalton Transactions . pp. 557-561. ISSN 1472-7773

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The title compound, [Os3(CO)9(NO)2], has been prepared by the reaction of NO with [Os3(CO)12] in n-octane at 126 °C. Carbon-13 n.m.r. spectroscopy indicates that the structure is derived from that of [Os3(CO)12] by the replacement of three CO ligands about one osmium by two terminally bound NO ligands. The stereodynamic behaviour of the molecule, as determined by 13C n.m.r. spectroscopy over a range of temperature, has been interpreted in terms of a process involving terminal-bridging NO interchange of the type previously observed for certain CO-cluster compounds. On reaction with ligands L (= NH3, NEtH2, and CO) the formation of the unstable adducts [Os3(CO)9(NO)2L] is observed; with L = P(OMe)3 or PPh3 the substituted complexes [Os3(CO)8(NO)2{P(OMe)3}] or [Os3(CO)9(NO)2(PPh3)] are produced. A single-crystal analysis of the trimethyl phosphite compound confirms that two terminally bound NO ligands are present. For L = pyridine (py), [Os3(CO)9(NO)2] forms the dinitrosyl-bridged compound [Os3(CO)92-NO)2(py)], quantitatively. The factors which govern the course of these reactions are discussed.

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ID Code:2207
Deposited On:08 Oct 2010 07:32
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