A heterobimetallic complex featuring a Ti–Co multiple bond and its application to the reductive coupling of ketones to alkenes

Wu, Bing; Bezpalko, Mark W.; Foxman, Bruce M.; Thomas, Christine M.

doi:10.1039/c4sc03772c

Title: A heterobimetallic complex featuring a Ti–Co multiple bond and its application to the reductive coupling of ketones to alkenes

Journal Article · Mon Jan 19 00:00:00 EST 2015 · Chemical Science

DOI:https://doi.org/10.1039/c4sc03772c· OSTI ID:1458515

Wu, Bing ^[1]; Bezpalko, Mark W. ^[1]; Foxman, Bruce M. ^[1]; Thomas, Christine M. ^[1]

Brandeis Univ., Waltham, MA (United States). Dept. of Chemistry

Here, we explore metal–metal multiple bonds between first row transition metals, Ti/Co complexes supported by two phosphinoamide ligands have been synthesized and characterized. The Ti metalloligand Cl₂Ti(XylNPiPr₂)₂ (1) was treated with CoI₂ under reducing conditions, permitting isolation of the Ti/Co complex [(μ-Cl)Ti(XylNPiPr₂)₂CoI]₂ (2). One electron reduction of complex 2 affords ClTi(XylNPiPr₂)₂CoPMe₃ (3), which features a metal–metal triple bond and an unprecedentedly short Ti–Co distance of 2.0236(9) Å. This complex is shown to promote the McMurry coupling reaction of aryl ketones into alkenes, with concomitant formation of the tetranuclear complex [Ti(μ₃-O)(NXylPiPr₂)₂CoI]₂ (4). A cooperative mechanism involving bimetallic C=O bond activation and a cobalt carbene intermediate is proposed.

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Research Organization:: Brandeis Univ., Waltham, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0004019

OSTI ID:: 1458515

Journal Information:: Chemical Science, Vol. 6, Issue 3; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 38 works

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