Triphenylmethyl Thionitrite: An Efficient NO Transfer Reagent During the Synthesis of a Triruthenium Nitrosyl Cluster

The synthesis and structural characterization of the novel triruthenium nitrosyl cluster [Ru3(μ‐NO)(CO)5(μ‐H)(μ‐PBut2)2(μ‐dppm)] (2) is described. Compound 2 was obtained by the reaction of the 46‐valence electron cluster [Ru3(μ‐CO)(CO)4(μ3‐H)(μ‐H)(μ‐PBut2)2(μ‐dppm)] (1) with nitric oxide and on the other hand in a more efficient way by the reaction of 1 with the nitrosyl transfer reagent triphenylmethyl thionitrite (TTN). The reaction of 1 with NO was outlined in dichloromethane whereas the reaction with TTN was realized in THF. Both methods worked at ambient temperature affording compound 2 in high yield. Temporarily we found that the transformation of 1 with NO was accompanied by a fast side‐reaction resulting in a further substitution of CO ligands. The molecular structure of 2 in the crystal was confirmed by single‐crystal X‐ray diffraction.