Opening the CoIII,IV2(μ-O)2 Diamond Core by Lewis Bases Leads to Enhanced C-H Bond Cleaving Reactivity

J Am Chem Soc. 2020 Dec 30;142(52):21670-21678. doi: 10.1021/jacs.0c07294. Epub 2020 Dec 16.

Abstract

The high-valent diiron(IV) intermediate Q is the key oxidant that cleaves strong C-H bonds of methane in the catalytic cycle of soluble methane monooxygenase (sMMO). sMMO-Q was previously reported as a bis-μ-oxo FeIV2(μ-O)2 diamond core but was recently described to have an open core with a long Fe···Fe distance. We recently reported a high-valent CoIII,IV2(μ-O)2 diamond core complex (1) that is highly reactive with sp3 C-H bonds. In this work, we demonstrated that the C-H bond cleaving reactivity of 1 can be further enhanced by introducing a Lewis base X, affording faster kinetic rate constants and the ability to cleave stronger C-H bonds compared to 1. We proposed that 1 first reacts with X in a fast equilibrium to form an open core species X-CoIII-O-CoIV-O (1-X). We were able to characterize 1-X using EPR spectroscopy and DFT calculations. 1-X exhibited an S = 1/2 EPR signal distinct from that of the parent complex 1. DFT calculations showed that 1-X has an open core with the spin density heavily delocalized in the CoIV-O unit. Moreover, 1-X has a more favorable thermodynamic driving force and a smaller activation barrier than 1 to carry out C-H bond activation reactions. Notably, 1-X is at least 4 orders of magnitude more reactive than its diiron open core analogues. Our findings indicate that the diamond core isomerization is likely a practical enzymatic strategy to unmask the strong oxidizing power of sMMO-Q necessary to attack the highly inert C-H bonds of methane.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Cobalt / chemistry*
  • Diamond / chemistry*
  • Hydrogen / chemistry*
  • Lewis Bases / chemistry*
  • Thermodynamics

Substances

  • Lewis Bases
  • Cobalt
  • Diamond
  • Hydrogen