Notizen: Zur Reaktion von Dikobaltoktacarbonyl mit Nitriloxiden und organischen Aziden

The First Chemical Achievements and Publications by Justus von Liebig (1803−1873) on Metal Fulminates and Some Further Developments in Metal Fulminates and Related Areas of Chemistry

“…[87] By reaction of stable nitrile oxides with zerovalent platinum complexes [(Ph 3 P) 2 Pt(L)] (L ϭ 2 ϫ PPh 3 , C 2 H 4 ) the nitrile oxide is deoxygenated and one of the phenyl groups on PPh 3 migrates to the platinum atom to give the complexes [(Ph 3 P)(RCN)Pt(OPPh 2 )(Ph)], [88] in which the OPPh 2 group is bonded by the P atom to the metal atom. The only complex in which an intact RCNO group is present appears to be the cluster [Cp 3 Co 3 (µ 3 -CR)(µ 2 -RCNO)] which is formed from Cp 3 Co 3 (µ 3 -CR) 2 and NO ϩ .…”

Non-Traditional Oxidants in Preparative Coordination Chemistry

“…Aromatic azo-and ami no-compounds were isolated and the transformation of CO into C0 2 noted. About five years later the ability of nitriloxides 175 and a number of aliphatic, aromatic, and heterocyclic compounds with N-O bonds 176 to oxygenate carbonyl ligands in cobalt and iron complexes was reported. It was suggested 176 that the oxidation of carbonyl ligands proceeds via nudeophilic attack by the oxygen atom donor on the carbonyl carbon atom which, as a result of coordination, has electrophilic character.…”