Reactivity of Cyanide and Thiocyanate Towards the Nitrosyl Carbonyl [Co(CO)3(NO)]: Reactivity of Cyanide and Thiocyanate Towards the Nitrosyl Carbonyl [Co(CO)3(NO)]

The reaction of equimolar amounts of [Co(CO)3(NO)] and [PPN]CN, PPN+ = (PPh3)2N+, in THF at room temperature resulted in ligand substitution of a carbonyl towards the cyanido ligand presumably affording the complex salt PPN[Co(CO)2(NO)(CN)] as a reactive intermediate species which could not be isolated. Applying the synthetic protocol using the nitrosyl carbonyl in excess, the title reaction afforded unexpectedly the novel complex salt PPN[Co2(μ‐CN)(CO)4(NO)2] (1) in high yield. Because of many disorder phenomena in crystals of 1 the corresponding NBu4+ salt of 1 has been prepared and the molecular structure of the dinuclear metal core in NnBu4[Co2(μ‐CN)(CO)4(NO)2] (2) was determined by X‐ray crystal diffraction in a more satisfactory manner. In contrast to the former result, the reaction of [PPN]SCN with [Co(CO)3(NO)] yielded the mononuclear complex salt PPN[Co(CO)2(NO)(SCN‐κN)] (3) in good yield whose molecular structure in the solid was even determined and its composition additionally confirmed by spectroscopic means.