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


ABSTRACT: To 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 [(?-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(?3-O)(NXylPiPr2)2CoI]2 (4). A cooperative mechanism involving bimetallic C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 O bond activation and a cobalt carbene intermediate is proposed.

SUBMITTER: Wu B 

PROVIDER: S-EPMC5654242 | biostudies-literature | 2015 Mar

REPOSITORIES: biostudies-literature

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

Wu Bing B   Bezpalko Mark W MW   Foxman Bruce M BM   Thomas Christine M CM  

Chemical science 20150119 3


To 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 Cl<sub>2</sub>Ti(XylNP<sup>i</sup>Pr<sub>2</sub>)<sub>2</sub> (<b>1</b>) was treated with CoI<sub>2</sub> under reducing conditions, permitting isolation of the Ti/Co complex [(μ-Cl)Ti(XylNP<sup>i</sup>Pr<sub>2</sub>)<sub>2</sub>CoI]<sub>2</sub> (<b>2</b>). One electron reduction of complex <b>2</b> afford  ...[more]

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