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The reactions of the title complex (1) with different p-block element (E) molecules was examined. Compound 1 reacted with BH 3 ·THF at room temperature to give the trihydride [W 2 Cp 2 (μ-H)H 2 (μ-PPh 2 )(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 HSnPh 3 , to give the related dihydride stannyl derivative [W 2 Cp 2 (μ-H)H(μ-PPh 2 )(NO) 2 (SnPh 3 )]. In contrast, the reaction of 1 with HSPh involved H 2 elimination to give the thiolate-bridged complex [W 2 Cp 2 (μ-SPh)(μ-PPh 2 )(NO) 2 ], while that with (p-tol)C(O)H resulted in insertion of the aldehyde to yield the related alkoxide complex [W 2 Cp 2 {μ-OCH 2 (p-tol)}(μ-PPh 2 )(NO) 2 ]. Insertion also prevailed in the reactions of 1 with CN  Bu, which, however, involved the competitive formation of new C-H or N-H bonds, to give a mixture of formimidoyl and aminocarbyne derivatives, [W 2 Cp 2 (μ-κ 1 :η 2 -HCN  Bu)(μ-PPh 2 )(NO) 2 ] (W-W = 3.0177(2) Å) and [W 2 Cp 2 {μ-C(NH  Bu)}(μ-PPh 2 )(NO) 2 ] (W-W = 2.9010(4) Å), 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 μ-κ 1 :η 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 [W 2 Cp 2 (μ-κ 1 :η 2 -CH 3 )(μ-PPh 2 )(NO) 2 ] (calculated W-W = 2.923 Å), whereas the reaction with N 2 CH(SiMe 3 ) proceeded with insertion of the diazoalkane to give the corresponding hydrazonide complex [W 2 Cp 2 {μ-NH(NCHSiMe 3 )}(μ-PPh 2 )(NO) 2 ] (W-W = 2.8608(4) Å). The latter was converted under alkaline conditions to the methyldiazenide derivative [W 2 Cp 2 {μ-N(NMe)}(μ-PPh 2 )(NO) 2 ] (W-W = 2.8730(2) Å), in a process involving hydrolysis of the C-Si bond coupled with a 1,3-H shift from N to C.

inorganic chemistry

E–H Bond Activation and Insertion Processes in the Reactions of the Unsaturated Hydride [W2Cp2(μ-H)(μ-PPh2)(NO)2]