Time-resolved IR studies on the mechanism for the functionalization of primary C-H bonds by photoactivated Cp*W(CO)3(Bpin)

Journal of the American Chemical Society
Karma R SawyerCharles B Harris

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 t...Continue Reading

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Citations

Nov 18, 2015·Journal of Chemical Theory and Computation·Lianrui Hu, Hui Chen
Sep 16, 2016·Journal of the American Chemical Society·F Mark ChadwickAndrew S Weller
Sep 10, 2014·Chemistry : a European Journal·Rowan D Young
Mar 18, 2011·Angewandte Chemie·Timothy Newhouse, Phil S Baran
Sep 29, 2012·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Weitao ZhuBo Chen
Jul 2, 2010·Organic & Biomolecular Chemistry·Georgiy B Shul'pin
May 31, 2012·Nature Communications·Holger BraunschweigAlfredo Vargas
Feb 18, 2021·Chemical Reviews·Ya-Ming TianTodd B Marder
Feb 23, 2021·The Journal of Physical Chemistry Letters·Christopher P GordonChristophe Copéret
Mar 20, 2010·Chemical Reviews·Holger BraunschweigAchim Schneider
Dec 12, 2018·Journal of the American Chemical Society·Christopher P GordonChristophe Copéret

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