Facile nitrosyl N-O bond cleavage upon thermolysis of Cp*W(NO)Ph2

Article abstract of DOI:10.1021/om00017a077

Thermolysis of Cp*W(NO)Ph₂ (1) in C₆H₆ at 60° C for 24 h affords the new nitrosyl N-O bond cleavage products Cp*W(η²-ONPh)(NPh)Ph (2) and [Cp*W(O)-Ph](μ-N)[Cp*W(NO)Ph] (3), as well as the known Cp*W(O)₂Ph (4), in isolated yields of 10, 9, and 30%, respectively. Complex 2 has been subjected to a single-crystal X-ray crystallographic analysis. Crystals of 2 are orthorhombic, space group Pcab, with a = 16.538(2) A?, b = 21.803(4) A?, c = 13.492(3) A? and Z = 8; the structure was solved by conventional heavy-atom methods and was refined by full-matrix least-squares procedures to R_F = 0.026 and R_wF = 0.024 for 2999 reflections having I ≥ 3σ(I). Also, thermolyses of Cp*W(NO)Ph₂ and Cp*W-(NO)(p-tolyl)₂ in the presence of PhSSPh result in quantitative conversion to Cp*W(NO)(Ar)(SPh) (Ar = Ph (5), p-tolyl (6), respectively).