Thermolysis of Cp*W(NO)Ph2 (1) in C6H6 at 60-degrees-C for 24 h affords the new nitrosyl N-0 bond cleavage products Cp*W(eta2-ONPh)(NPh)Ph (2) and [Cp*W(O)Ph](mu-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) angstrom, b = 21.803(4) angstrom, c = 13.492(3) angstrom 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 greater-than-or-equal-to 3sigma(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).