Why Two Metals Are Better Than One for Heterodinuclear Cobalt–Zirconium-Catalyzed Kumada Coupling

doi:10.1021/acs.organomet.8b00449

Title: Why Two Metals Are Better Than One for Heterodinuclear Cobalt–Zirconium-Catalyzed Kumada Coupling

Abstract

Heterodinuclear transition metal complexes with a direct metal–metal interaction offer the potential of unique reactivity compared with mononuclear catalysts. Heterodinuclear Co–Zr complexes with phosphinoamide ligands bridging Co and Zr metal centers are effective precatalysts for Kumada C–C bond coupling reactions between alkyl halides and alkyl Grignards. On the other hand, the analogous mononuclear Co tris(phosphinoamine) complex without Zr provides very inefficient catalysis. Here we describe density functional theory calculations that reveal the mechanistic and reactivity impact of the Co–Zr metal–metal interaction and phosphinoamide ligands on alkyl halide–alkyl Grignard Kumada coupling catalysis. The Co–Zr interaction enables two-electron reduction of the precatalyst to form an active catalyst, which then allows a low-energy electron-transfer alkyl halide oxidative addition mechanism. The Co–Zr interaction and the phosphinoamide ligands bridging the metal centers provide a dialkyl intermediate with a low-energy C–C bond forming reductive elimination route through a phosphine dissociation pathway, which is not viable for an analogous mononuclear Co complex.

Authors:

Coombs, Jimmy ^[1]; Perry, Dalton ^[1]; Kwon, Doo-Hyun ^[1];

^[2];

^[1]

Brigham Young Univ., Provo, UT (United States)
The Ohio State Univ., Columbus, OH (United States)

Publication Date:: 2018-11-08

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

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

OSTI Identifier:: 1524783

Grant/Contract Number:: [SC0014151]

Resource Type:: Accepted Manuscript

Journal Name:: Organometallics

Additional Journal Information:: [ Journal Volume: 37; Journal Issue: 22]; Journal ID: ISSN 0276-7333

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Coombs, Jimmy, Perry, Dalton, Kwon, Doo-Hyun, Thomas, Christine M., and Ess, Daniel H. Why Two Metals Are Better Than One for Heterodinuclear Cobalt–Zirconium-Catalyzed Kumada Coupling.  United States: N. p., 2018. 
        Web.  doi:10.1021/acs.organomet.8b00449.

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                    Coombs, Jimmy, Perry, Dalton, Kwon, Doo-Hyun, Thomas, Christine M., & Ess, Daniel H. Why Two Metals Are Better Than One for Heterodinuclear Cobalt–Zirconium-Catalyzed Kumada Coupling.  United States.  doi:10.1021/acs.organomet.8b00449.

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                    Coombs, Jimmy, Perry, Dalton, Kwon, Doo-Hyun, Thomas, Christine M., and Ess, Daniel H. Thu .  
        "Why Two Metals Are Better Than One for Heterodinuclear Cobalt–Zirconium-Catalyzed Kumada Coupling".  United States.  doi:10.1021/acs.organomet.8b00449.  https://www.osti.gov/servlets/purl/1524783.

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@article{osti_1524783,

  title        = {Why Two Metals Are Better Than One for Heterodinuclear Cobalt–Zirconium-Catalyzed Kumada Coupling},

  author       = {Coombs, Jimmy and Perry, Dalton and Kwon, Doo-Hyun and Thomas, Christine M. and Ess, Daniel H.},

  abstractNote = {Heterodinuclear transition metal complexes with a direct metal–metal interaction offer the potential of unique reactivity compared with mononuclear catalysts. Heterodinuclear Co–Zr complexes with phosphinoamide ligands bridging Co and Zr metal centers are effective precatalysts for Kumada C–C bond coupling reactions between alkyl halides and alkyl Grignards. On the other hand, the analogous mononuclear Co tris(phosphinoamine) complex without Zr provides very inefficient catalysis. Here we describe density functional theory calculations that reveal the mechanistic and reactivity impact of the Co–Zr metal–metal interaction and phosphinoamide ligands on alkyl halide–alkyl Grignard Kumada coupling catalysis. The Co–Zr interaction enables two-electron reduction of the precatalyst to form an active catalyst, which then allows a low-energy electron-transfer alkyl halide oxidative addition mechanism. The Co–Zr interaction and the phosphinoamide ligands bridging the metal centers provide a dialkyl intermediate with a low-energy C–C bond forming reductive elimination route through a phosphine dissociation pathway, which is not viable for an analogous mononuclear Co complex.},

  doi          = {10.1021/acs.organomet.8b00449},

  journal      = {Organometallics},

  number       = [22],

  volume       = [37],

  place        = {United States},

  year         = {2018},

  month        = {11}

}

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DOI: 10.1021/acs.organomet.8b00449

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Title: Why Two Metals Are Better Than One for Heterodinuclear Cobalt–Zirconium-Catalyzed Kumada Coupling

Abstract

Citation Formats

Rare-earth/zinc heterometallic complexes containing both alkoxy-amino-bis(phenolato) and chiral salen ligands: synthesis and catalytic application for copolymerization of CO 2 with cyclohexene oxide journal, January 2019

Rare-earth/zinc heterometallic complexes containing both alkoxy-amino-bis(phenolato) and chiral salen ligands: synthesis and catalytic application for copolymerization of CO ₂ with cyclohexene oxide
journal, January 2019