title: Time-resolved IR studies on the mechanism for the functionalization of primary C-H bonds by photoactivated Cp*W(CO)3(Bpin).
abstract: 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)(CH(3))(5); pin = 1,2-O(2)C(2)-(CH(3))(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 sigma-bond metathesis mechanism--in 16 micros, a terminal hydrogen on pentane appears to migrate to the Bpin ligand to form a sigma-borane complex, Cp*W(CO)(2)(H-Bpin)(C(5)H(11)). Our data imply that the borane ligand rotates until the boron is directly adjacent to the C(5)H(11) 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)(C(5)H(11)-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 micros. 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.
authors.affiliation: Department of Chemistry, University of California, Berkeley, California 94720, USA.
authors.forename: Karma R
authors.initials: KR
authors.lastname: Sawyer
authors.forename: James F
authors.initials: JF
authors.lastname: Cahoon
authors.forename: Jennifer E
authors.initials: JE
authors.lastname: Shanoski
authors.forename: Elizabeth A
authors.initials: EA
authors.lastname: Glascoe
authors.forename: Matthias F
authors.initials: MF
authors.lastname: Kling
authors.forename: Jacob P
authors.initials: JP
authors.lastname: Schlegel
authors.forename: Matthew C
authors.initials: MC
authors.lastname: Zoerb
authors.forename: Marko
authors.initials: M
authors.lastname: Hapke
authors.forename: John F
authors.initials: JF
authors.lastname: Hartwig
authors.forename: Charles Edwin
authors.initials: CE
authors.lastname: Webster
authors.forename: Charles B
authors.initials: CB
authors.lastname: Harris