Summary
Carbon monoxide reacts with the cationic dinitrosyls [M(NO)2(PPh3)2]+ (M = Rh, Ir) under ambient conditions to produce CO2, N2O and the tricarbonyl cations, (M(CO)3(PPh3)2]+. The cationic tricarbonyls are reconverted into the dinitrosyl reactants on treatment with NO atca. 80°. The Ru(NO)2(PPh3)2 and Os(NO)2(PPh3)2 complexes react similarly with CO but under more vigorous conditions whereas the corresponding dinitrosyls of cobalt and iron do not undergo this reaction under similar conditions. A pentacoordinate dinitrosyl intermediate [M(NO)2(CO)(PPh3)2]n+ is proposed and a mechanism for the catalytic oxidation of CO by NO is presented. Studies of Pt(N2O2)PPh3)2 establish that a dinitrogcn dioxide intermediate, produced by the coupling of two nitrosyl ligands, is reasonable.
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References
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Bhaduri, S., Johnson, B.F.G. Transition metal nitrosyl compounds. Part XIV(1). The oxidation of carbon monoxide by nitric oxide using [M(NO)2(PPh3)2]n+ (M=Fe, Ru or Os; n=0. M=Co, Rh or Ir; n=1). Transition Met Chem 3, 156–161 (1978). https://doi.org/10.1007/BF01393534
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DOI: https://doi.org/10.1007/BF01393534