Oxygen Atom Transfer from Coordinated Nitrite Ligands

OXYGEN ATOM TRANSFER FROM COORDINATED NITRITE LIGANDS 

Transfer from Meta Nitrites to Carbon Monoxide and Triphenylphosphine 

The reaction of nitrite complexes with carbon monoxide to yield the metal nitrosyl complex and carbon dioxide has been known for a consider- 

The reaction is rapid under ambient conditions, and further work has shown that the PE 3 ligand can be replaced by dppe, PMe2Ph, Ph2PCH = CHPPh2/ The rate law for the reaction is -d[Ni N02)2L2]/dt = / 2[Ni(N02)2i 2][C0], and an associative mechanism (45) is proposed. 

A similar reaction with Pd(N02)2(PMePh2)2 and CO produces CO2 and the cluster compound Pd4(CO)5(PMePh2)4- Further work on this reaction using oxygen-18-labeled nitrite has confirmed this ligand to be the source of oxygen, and a cyclic intermediate is proposed for the oxygen transfer step.  

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