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

Abstract

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.

Authors:
 [1];  [1];  [1];  [1]
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  1. Brandeis Univ., Waltham, MA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Brandeis Univ., Waltham, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1458515
Grant/Contract Number:  
SC0004019
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 6; Journal Issue: 3; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Wu, Bing, Bezpalko, Mark W., Foxman, Bruce M., and Thomas, Christine M. A heterobimetallic complex featuring a Ti–Co multiple bond and its application to the reductive coupling of ketones to alkenes. United States: N. p., 2015. Web. doi:10.1039/c4sc03772c.
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Wu, Bing, Bezpalko, Mark W., Foxman, Bruce M., & Thomas, Christine M. A heterobimetallic complex featuring a Ti–Co multiple bond and its application to the reductive coupling of ketones to alkenes. United States. https://doi.org/10.1039/c4sc03772c
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Wu, Bing, Bezpalko, Mark W., Foxman, Bruce M., and Thomas, Christine M. Mon . "A heterobimetallic complex featuring a Ti–Co multiple bond and its application to the reductive coupling of ketones to alkenes". United States. https://doi.org/10.1039/c4sc03772c. https://www.osti.gov/servlets/purl/1458515.
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@article{osti_1458515,
title = {A heterobimetallic complex featuring a Ti–Co multiple bond and its application to the reductive coupling of ketones to alkenes},
author = {Wu, Bing and Bezpalko, Mark W. and Foxman, Bruce M. and Thomas, Christine M.},
abstractNote = {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.},
doi = {10.1039/c4sc03772c},
journal = {Chemical Science},
number = 3,
volume = 6,
place = {United States},
year = {Mon Jan 19 00:00:00 EST 2015},
month = {Mon Jan 19 00:00:00 EST 2015}
}
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https://doi.org/10.1039/c4sc03772c
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Cited by: 38 works
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Figures / Tables:

Scheme 1 Scheme 1: Justification for exploring a bis(phosphinoamide) ligand framework for heterobimetallic complexes.
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      Figures / Tables found in this record:

      Scheme 1 (p. 1)figure
      Fig. 1 (p. 2)figure
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      Fig. 3 (p. 3)figure
      Table 1 (p. 3)table
      Figure-4 (p. 4)figure
      Scheme 3 (p. 4)figure
      Scheme 4 (p. 5)figure
      Scheme 5 (p. 5)figure
      Table 2 (p. 5)table
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