Reactions of HW2(CO)9(NO) and HW2(CO)7(THF)2(NO) with excess RNC (R = Me, (t)Bu, PhCH2, (i)Pr) yields a yellow complex HW2(CO)7(RNC)2(NOax) (ax = axial) and its isomeric reddish complex HW2(CO)7(RNC)2(NOeq) (eq = equatorial). Both bent-staggered and bent-eclipsed conformations are found to exist in these isomers. Treatment of complexes HW2(CO)9(NO), HW2(CO)8(PPh3)(NO), HW2(CO)7(MeNC)2(NOax), and HW2(CO)7(MeNC)2(NOeq) with Ph3P=NR (R = (i)Pr, (n)Pr, Ph, (t)Bu) yields HW2(CO)8(RNC)(NOax) (R = (i)Pr, Ph, (t)Bu), HW2(CO)7(RNC)2(NOax) (R = (i)Pr, Ph), HW2(CO)7(PPh3)(nPrNC)(NOax), HW2(CO)6(PPh3)(nPrNC)2(NOax), and HW2(CO)6(MeNC)2(nPrNC)(NOeq). There is no rearrangement, which is found in the reaction of HW2(CO)9(NO) with RNC, of ligands during the conversion of coordinated CO ligands to RNC by Ph3PNR in these reactions. Electronic and steric influences on the sequential conversion of CO to RNC are supported by crystal structures determinations of several new complexes. Crystal data for HW2(CO)8(PhNC)(NOax): C15H6N2O9W2; P2(1)/c (monoclinic); a = 10.802(2), b = 11.705(1), c = 16.695(2) angstrom; beta = 108.67(1)degrees; Z = 4; R = 0.031, R(w) = 0.032. HW2(CO)6(PhNC)(nPrNC)2(NOax): C21H20N4O7W2; P1 (triclinic); a = 8.718(1), b = 11.135(2); c = 13.832(1) angstrom; alpha = 92.24(1), beta = 79.58(1), gamma = 91.53(1)degrees; Z = 2; R = 0.031, R(w) = 0.032. HW2(CO)6(MeNC)2(nPrNC)(NOeq): C14H14N4O7W2; P1 (triclinic); a = 10.140(2); b = 10.147(2); c = 11.346(2) angstrom; alpha = 84.34(2), beta = 112.86(2), gamma = 100.92(1)degrees; Z = 2; R = 0.033, R(w) = 0.037.