Exploring the Alcohol Stability of Bis(phosphine) Cobalt Dialkyl Precatalysts in Asymmetric Alkene Hydrogenation

Zhong, Hongyu; Friedfeld, Max R.; Camacho-Bunquin, Jeffrey; Sohn, Hyuntae; Yang, Ce; Delferro, Massimiliano; Chirik, Paul J.

doi:10.1021/acs.organomet.8b00516

Exploring the Alcohol Stability of Bis(phosphine) Cobalt Dialkyl Precatalysts in Asymmetric Alkene Hydrogenation

Journal Article · Mon Nov 05 00:00:00 EST 2018 · Organometallics

DOI:https://doi.org/10.1021/acs.organomet.8b00516· OSTI ID:1481713

^[1]; Friedfeld, Max R. ^[2]; ^[3]; Sohn, Hyuntae ^[3]; Yang, Ce ^[3]; ^[3]; ^[2]

Princeton Univ., Princeton, NJ (United States); Argonne National Laboratory
Princeton Univ., Princeton, NJ (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)

Here, cobalt complexes bearing enantiopure, bidentate bis(phosphine) ligands exhibit extraordinary activity and stereoselectivity for the hydrogenation of enamides. Optimal performance was observed in polar protic solvents such as methanol, an industrially preferred green solvent but a medium that is often a poison for reduced Earth abundant metals. The interaction of the low spin cobalt(II) dialkyl complex, (R,R)-(ⁱPr-DuPhos)Co(CH₂SiMe₃)₂ with alcohols including: 4-methoxyphenol, pinacol, and CH₃OH was studied. With the alcohols lacking beta-hydrogens, cobalt bis(alkoxide) complexes were isolated and structurally characterized. With methanol, protonolysis of the alkyl ligands was again observed followed by dehydrogenation of the alcohol and [(R,R)-(ⁱPr-DuPhos)Co]₂(mu-CO)₂ was isolated. Both solid-state and solution EXAFS studies were conducted to establish the spectroscopic signatures of bis(phosphine)cobalt(II) and cobalt(0) complexes relevant to catalytic hydrogenation and also to probe the role of phosphine dissociation in methanol.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1481713

Alternate ID(s):: OSTI ID: 1493760

Journal Information:: Organometallics, Journal Name: Organometallics Journal Issue: 1 Vol. 38; ISSN 0276-7333

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Syntheses and Catalytic Hydrogenation Performance of Cationic Bis(phosphine) Cobalt(I) Diene and Arene Compounds Zhong, Hongyu; Friedfeld, Max R.; Chirik, Paul J. Angewandte Chemie, Vol. 131, Issue 27 https://doi.org/10.1002/ange.201903766	journal	May 2019
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Exploring the Alcohol Stability of Bis(phosphine) Cobalt Dialkyl Precatalysts in Asymmetric Alkene Hydrogenation

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