Variable-temperature (31)P{(1)H} NMR spectroscopy of the agostic complexes M(CO)(3)(PCy(3))(2) (M = Mo, W) indicates dynamic behavior as evidenced by collapse below -20 degrees C of a singlet to an AB signal plus a shifted singlet. The inequivalency of the phosphines is possibly due to the presence of conformational isomers resulting from hindered rotation of the M-P bond or, less likely, a geometric isomer with pseudo-cis PCy(3) ligands. Further studies on the coordination chemistry of W(CO)(3)(PR(3))(2) (R = iPr, Cy) were performed. The bridging dinitrogen complex [W(CO)(3)(PiPr(3))(2)](2)(&mgr;-N(2)) (1) was cleanly formed in the reaction of W(CO)(3)(PiPr(3))(2) with N(2). Complex 1 was structurally characterized and compared with other bridging dinitrogen compounds of tungsten. The ethylene complex W(CO)(3)(PCy(3))(2)(eta(2)-C(2)H(4)) (2) was synthesized and characterized by X-ray crystallography in order to compare the binding mode of ethylene with that of H(2). Phenylsilane reacted with W(CO)(3)(PR(3))(2) (R = iPr, Cy) to form the thermally unstable oxidative addition (OA) products WH(SiH(2)Ph)(CO)(3)(PR(3))(2) (3, R = Cy; 4, R = iPr). Diphenylsilane reacted with W(CO)(3)(PiPr(3))(2) at 60 degrees C to form the bridging silyl species [W(CO)(3)(PiPr(3))(&mgr;-SiHPh(2))](2) (5), which was confirmed by spectroscopic techniques and X-ray crystallography to have two 3-center 2-electron W.H.Si interactions. Detailed comparisons of the binding and activation of silanes versus H(2) on various 16e metal centers suggest a high degree of similarity, but relative ease of OA depends on the electrophilicity of the metal-ligand fragment and other factors such as bond energetics. Increasing the electrophilicity of the metal center (e.g., adding positive charge) may aid in stabilizing alkane coordination.