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) |
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| Authors: | Sumit Bhaduri Brian F G Johnson |
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| Institution: | (1) University Chemical Laboratory, Lensfield Road, CB2 1EW Cambridge, UK |
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| Abstract: | 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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