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S M L C 1 0 2 Aliphatic C-H Bond Activation O c t o b e r ...

Date post: 26-Mar-2022
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High-valent Co2(μ-O)2 Diamond Core Complexes: New Bio-inspired Strategies for Aliphatic C-H Bond Activation Presented By: Dr. Dong Wang University of Montana The activation of carbon-hydrogen (C–H) bonds is the first step of functionalizing hydrocarbons. This transformation is a key step in many biological and synthetic processes. Soluble methane monooxygenase (sMMO) is a representative example of nonheme dinuclear iron enzymes that hydroxylate strong aliphatic C-H bonds at mild conditions by a high-valent FeIV2(μ-O)2 “diamond core” intermediate. One of our research thrust is to develop bio-inspired high-valent M2(μ- O)2 complexes of late-transition metals for activating and functionalizing inert aliphatic C-H bonds. Recently, we generated a mixed-valent CoIII,IV2(μ-O)2 species by one-electron oxidation of its CoIII2(μ-O)2 precursor, and characterized it by combined spectroscopic and computational approaches. Interestingly, this high-valent species cleaves strong aliphatic C-H bonds with decent rate constants even at cryo-temperatures to afford the oxygenated products in quantitative yields. This effort will lead to the development of more effective approaches for aliphatic C-H bond functionalization and new discoveries of the high-valent diamond core chemistry for late-transition metals in the near future. October 4 - 4 PM SMLC 102
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High-valent Co2(μ-O)2 Diamond CoreComplexes: New Bio-inspired Strategies for

Aliphatic C-H Bond ActivationPresented By: Dr. Dong Wang

University of Montana

The activation of carbon-hydrogen (C–H) bonds is the first step of functionalizing hydrocarbons.This transformation is a key step in many biological and synthetic processes. Soluble methanemonooxygenase (sMMO) is a representative example of nonheme dinuclear iron enzymes thathydroxylate strong aliphatic C-H bonds at mild conditions by a high-valent FeIV2(μ-O)2 “diamondcore” intermediate. One of our research thrust is to develop bio-inspired high-valent M2(μ-O)2 complexes of late-transition metals for activating and functionalizing inert aliphatic C-H bonds.Recently, we generated a mixed-valent CoIII,IV2(μ-O)2 species by one-electron oxidation of itsCoIII2(μ-O)2 precursor, and characterized it by combined spectroscopic and computationalapproaches. Interestingly, this high-valent species cleaves strong aliphatic C-H bonds with decentrate constants even at cryo-temperatures to afford the oxygenated products in quantitative yields.This effort will lead to the development of more effective approaches for aliphatic C-H bondfunctionalization and new discoveries of the high-valent diamond core chemistry for late-transitionmetals in the near future.

October 4 - 4 PMSMLC 102

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