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

Journal Article · · Organometallics

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.

Research Organization:
Brandeis Univ., Waltham, MA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
SC0014151
OSTI ID:
1524783
Journal Information:
Organometallics, Journal Name: Organometallics Journal Issue: 22 Vol. 37; ISSN 0276-7333
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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  • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n
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