A DFT Survey of the Effects of d‐Electron Count and Metal Identity on the Activation and Functionalization of C−H Bonds for Mid to Late Transition Metals

Moulder, Catherine A.; Cundari, Thomas R.

doi:10.1002/ijch.201700066

Title: A DFT Survey of the Effects of d‐Electron Count and Metal Identity on the Activation and Functionalization of C−H Bonds for Mid to Late Transition Metals

Journal Article · Thu Sep 21 00:00:00 EDT 2017 · Israel Journal of Chemistry

DOI:https://doi.org/10.1002/ijch.201700066· OSTI ID:1393689

^[1]; Cundari, Thomas R. ^[1]

University of North Texas, Department of Chemistry Center for Advanced Scientific Computing and Modeling (CASCaM) 1155 Union Circle #305070 Denton, Texas 76203–5017 United States

Abstract The contribution of metal identity to the activation and functionalization of methane by a series of three‐coordinate imide complexes is evaluated in silico for a 3‐by‐3 block of metals from Fe to Pt. Three mechanisms were studied: oxidative addition (OA) to the metal; hydrogen atom abstraction (HAA) by the imide nitrogen; and, [2+2] addition across the metal‐imide bond. In no studied case, was a [2+2] mechanism preferred, perhaps suggesting this mechanism is largely (entirely?) the domain of d ⁰ imides. There is a diagonal relationship within the nonet of metals studied in that OA is preferred for earlier, heavier (5d) members of the series, transitioning to an HAA mechanism for later, lighter (3d) imides. DFT indicates that important parameters in partitioning between HAA and OA mechanisms include the strength of the metal‐imide π‐bond, the ability of larger metals to accommodate increases in formal oxidation state and coordination number, and the soft acid/base compatibility of larger transition metals with soft hydride and methyl ligands

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Sponsoring Organization:: USDOE

Grant/Contract Number:: FG02-03ER15387

OSTI ID:: 1393689

Journal Information:: Israel Journal of Chemistry, Journal Name: Israel Journal of Chemistry Vol. 57 Journal Issue: 10-11; ISSN 0021-2148

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Israel

Language:: English

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Cited by: 7 works

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