Time-resolved infrared (TRIR) study on the formation and reactivity of organometallic methane and ethane complexes in...

We have used fast time-resolved infrared spectroscopy to characterize a series of organometallic methane and ethane complexes in solution at room temperature: W(CO)5(CH4) and M(eta5-C5R5)(CO)2(L) [where M = Mn or Re, R = H or CH3 (Re only); and L = CH4 or C2H6]. In all cases, the methane complexes are found to be short-lived and significantly more reactive than the analogous n-heptane complexes. Re(Cp)(CO)2(CH4) and Re(Cp*)(CO)2(L) [Cp* = eta5-C5(CH3)(5) and L = CH4, C2H6] were found to be in rapid equilibrium with the alkyl hydride complexes. In the presence of CO, both alkane and alkyl hydride complexes decay at the same rate. We have used picosecond time-resolved infrared spectroscopy to directly monitor the photolysis of Re(Cp*)(CO)3 in scCH4 and demonstrated that the initially generated Re(Cp*)(CO)2(CH4) forms an equilibrium mixture of Re(Cp*)(CO)2(CH4)/Re(Cp*)(CO)2(CH3)H within the first few nanoseconds (tau = 2 ns). The ratio of alkane to alkyl hydride complexes varies in the order Re(Cp)(CO)2(C2H6):Re(Cp)(CO)2(C2H5)H > Re(Cp*)(CO)2(C2H6):Re(Cp*)(CO)2(C2H5)H approximately equal to Re(Cp)(CO)2(CH4):Re(Cp)(CO)2(CH3)H > Re(Cp*)(CO)2(CH4):Re(Cp*)(CO)2(CH3)H. Activation parameters for the reactions of the organometallic methane and ethane complexes with CO have been measured, and the DeltaH++ values represent lower limits for the CH4 binding enthalpies to the metal center of W-CH4 (30 kJ.mol(-1)), Mn-CH4 (39 kJ.mol(-1)), and Re-CH4 (51 kJ.mol(-1)) bonds in W(CO)5(CH4), Mn(Cp)(CO)2(CH4), and Re(Cp)(CO)2(CH4), respectively.