Recently, transition-metal-boryl compounds have been reported that selectively functionalize primary C-H bonds in alkanes in high yield. We have investigated this process with one of the well-defined systems that reacts under photochemical conditions using both density functional theory calculations and pico- through microsecond time-resolved IR spectroscopy UV irradiation of Cp*W(CO)(3)(Bpin) (Cp* = C-5(CH3)(5), pin = 1,2-O2C2-(CH3)(4)) in neat pentane solution primarily results in dissociation of a single CO ligand and solvation of the metal by a pentane molecule from the bath within 2 ps. The spectroscopic data imply that the resulting complex, cis-Cp*W(CO)(2)(Bpin)(pentane), undergoes C-H bond activation by a cr-bond metathesis mechanism-in 16 mu s, a terminal hydrogen on pentane appears to migrate to the Bpin ligand to form a a-borane complex, Cp*W(CO)(2)(H-Bpin)(C5H11). Our data imply that the borane ligand rotates until the boron is directly adjacent to the C5H11 ligand. In this configuration, the B-H sigma-bond is broken in favor of a B-C sigma-bond, forming Cp*W(CO)(2)(H)(C5H11-Bpin), a tungsten-hydride complex containing a weakly bound alkylboronate ester The ester is then eliminated to form Cp*W(CO)(2)(H) in approximately 170 mu s We also identify two side reactions that limit the total yield of bond activation products and explain the 72% yield previously reported for this complex