The reactions of the title complex (1) with different p-block element (E) molecules was examined. Compound 1 reacted with BH3 center dot THF at room temperature to give the trihydride [W2Cp2(mu-H)H-2(mu-PPh2)(NO)(2)], which formally results from hydrogenation of 1, a reaction that actually does not take place when neat dihydrogen is used. Clean E-H bond oxidative addition, however, took place when 1 was reacted with HSnPh3, to give the related dihydride stannyl derivative [W2Cp2(mu-H)H(mu-PPh2)(NO)(2)(SnPh3)]. In contrast, the reaction of 1 with HSPh involved H-2 elimination to give the thiolate-bridged complex [W2Cp2(mu-SPh)(mu-PPh2)(NO)(2)], while that with (p-tol)C(O)H resulted in insertion of the aldehyde to yield the related alkoxide complex [W2Cp2{mu-OCH2(p-tol)}(mu-PPh2)(NO)(2)]. Insertion also prevailed in the reactions of 1 with (CNBu)-Bu-t, which, however, involved the competitive formation of new C-H or N-H bonds, to give a mixture of formimidoyl and aminocarbyne derivatives, [W2Cp2(mu-kappa(1):eta(2)-(HCNBu)-Bu-t)(mu-PPh2)(NO)(2)] (W-W = 3.0177(2) angstrom) and [W2Cp2{mu-C((NHBu)-Bu-t)}(mu-PPh2)(NO)(2)] (W-W = 2.9010(4) angstrom), respectively, even though the latter was thermodynamically preferred, according to density functional theory calculations. The former represents the first structurally characterized complex displaying a formimidoyl or iminoacyl ligand in the alkenyl-like mu-kappa(1):eta(2) coordination mode. The reaction of 1 with diazomethane proceeded with N-2 elimination and C-H coupling to yield the agostic methyl-bridged complex [W2Cp2(mu-kappa(1):eta(2)-CH3)(mu-PPh2)(NO)(2)] (calculated W-W = 2.923 angstrom), whereas the reaction with N2CH(SiMe3) proceeded with insertion of the diazoalkane to give the corresponding hydrazonide complex [W2Cp2{mu-NH(NCHSiMe3)}(mu-PPh2)(NO)(2)] (W-W = 2.8608(4) angstrom). The latter was converted under alkaline conditions to the methyldiazenide derivative [W2Cp2{mu-N(NMe)}(mu-PPh2)(NO)(2)] (W-W = 2.8730(2) angstrom), in a process involving hydrolysis of the C-Si bond coupled with a 1,3-H shift from N to C.