Photochemical Tungsten–Carbon Bond Cleavage in Bicyclic Tungstacyclopentanes

Journal of the American Chemical Society 2026

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Authors: René Riedel, Robert J. Dillon, Logan Trowbridge, Shankar Ramaswamy, Vivek Vasudev, Marielle Sewell, Veronica Carta, Mariona Sodupe, Xavier Solans‐Monfort, Christopher J. Bardeen, Richard R. Schrock, Matthew P. Conley
DOI: 10.1021/jacs.5c19313
Cited by: 0
References: 53

Abstract

W(NCPh 3 )(OSiPh 3 ) 2 (C 7 H 12 ) ( 1 ) and W(NAd)(OSiPh 3 ) 2 (C 7 H 12 ) ( 2 ) undergo photochemical α-hydrogen abstraction to form alkylidenes. Transient absorption studies suggest that fast W–C homolysis precedes thermal α-hydrogen abstraction. Radical trapping experiments in the presence of 5,5-dimethyl-1-pyrroline- N -oxide (DMPO) support formation of an alkyl radical in these reactions. DFT calculations of models of 1 and 2 are also consistent with formation of W(V)-alkyl-radical intermediates that ultimately abstract an α-hydrogen to form the alkylidene. This study provides evidence for W–C bond cleavage in reactions that convert catalytically inactive d 0 tungstacyclopentanes into metathesis-active alkylidenes.

Fields of Study & Subjects

Radical Photochemical Reactions Metalloenzymes and iron-sulfur proteins Synthetic Organic Chemistry Methods

Publication details

Journal / source
Journal of the American Chemical Society
Volume
148
Issue
2
Pages
2108–2113
Publication date
6 January 2026
Language
EN