Reactions of d(0) tungsten alkylidyne complexes with O2 or H2O. Formation of an oxo siloxy complex through unusual silyl migrations.

(Me3SiCH2)3(Me3SiC≡)W←O=PMe3 (1), an adduct between (Me3SiCH2)3W≡CSiMe3 (2) and O=PMe3, reacts with O2 to give O=W(OSiMe3)(CH2SiMe3)3 (3) and CO2. Reaction of 2 with H2O yields 3 and the trimer [(μ-O)W(CH2SiMe3)2(=O)(THF)]3 (4). In the reaction of D2O with 2, 3-d(n) and methane isotopologues CH2D2, CHD3 and CD4 have been observed.

Preparation of tungsten alkyl alkylidene alkylidyne complexes and kinetic studies of their formation.

An equilibrium mixture of alkyl alkylidyne W(CH2SiMe3)3(CSiMe3)(PMe3) (1a) and its bis(alkylidene) tautomer W(CH2SiMe3)2(=CHSiMe3)2(PMe3) (1b) has been found to undergo an alpha-hydrogen abstraction reaction in the presence of PMe3 to form alkyl alkylidene alkylidyne W(CH2SiMe3)(=CHSiMe3)(CSiMe3)(PMe3)2 (2). In the presence of PMe3, the formation of 2 follows first-order kinetics, and the observed rate constant was found to be independent of the concentration of PMe3. The activation parameters for the formation of 2 are Delta H = 28.

An unusual exchange between alkylidyne alkyl and bis(alkylidene) tungsten complexes promoted by phosphine coordination: kinetic, thermodynamic, and theoretical studies.

d0 Tungsten alkylidyne alkyl complex (Me3SiCH2)3W(CSiMe3)(PMe3) (4a) was found to undergo a rare, PMe3-promoted exchange with its bis(alkylidene) tautomer (Me3SiCH2)2W(=CHSiMe3)2(PMe3) (4b). Thermodynamic studies of the exchange showed that 4b is favored and gave Keq and the enthalpy and entropy of the equilibrium: DeltaH degrees = -1.8(0.