Syntheses and Catalytic Hydrogenation Performance of Cationic Bis(phosphine) Cobalt(I) Diene and Arene Compounds

Hongyu Zhong; Max R. Friedfeld; Paul J. Chirik

doi:10.1002/anie.201903766

Syntheses and Catalytic Hydrogenation Performance of Cationic Bis(phosphine) Cobalt(I) Diene and Arene Compounds

Hongyu Zhong
, Max R. Friedfeld
, Paul J. Chirik

Chemistry

Research output: Contribution to journal › Article › peer-review

60 Scopus citations

Abstract

Chloride abstraction from [(R,R)-(^iPrDuPhos)Co(μ-Cl)]₂ with NaBAr^F₄ (BAr^F₄=B[(3,5-(CF₃)₂)C₆H₃]₄) in the presence of dienes, such as 1,5-cyclooctadiene (COD) or norbornadiene (NBD), yielded long sought-after cationic bis(phosphine) cobalt complexes, [(R,R)-(^iPrDuPhos)Co(η²,η²-diene)][BAr^F₄]. The COD complex proved substitutionally labile undergoing diene substitution with tetrahydrofuran, NBD, or arenes. The resulting 18-electron, cationic cobalt(I) arene complexes, as well as the [(R,R)-(^iPrDuPhos)Co(diene)][BAr^F₄] derivatives, proved to be highly active and enantioselective precatalysts for asymmetric alkene hydrogenation. A cobalt–substrate complex, [(R,R)-(^iPrDuPhos)Co(MAA)][BAr^F₄] (MAA=methyl 2-acetamidoacrylate) was crystallographically characterized as the opposite diastereomer to that expected for productive hydrogenation demonstrating a Curtin–Hammett kinetic regime similar to rhodium catalysis.

Original language	English (US)
Pages (from-to)	9194-9198
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	58
Issue number	27
DOIs	https://doi.org/10.1002/anie.201903766
State	Published - Jul 1 2019

All Science Journal Classification (ASJC) codes

General Chemistry
Catalysis

Keywords

alkene hydrogenation
asymmetric catalysis
catalyst–substrate complex
cobalt

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title = "Syntheses and Catalytic Hydrogenation Performance of Cationic Bis(phosphine) Cobalt(I) Diene and Arene Compounds",

abstract = "Chloride abstraction from [(R,R)-(iPrDuPhos)Co(μ-Cl)]2 with NaBArF4 (BArF4=B[(3,5-(CF3)2)C6H3]4) in the presence of dienes, such as 1,5-cyclooctadiene (COD) or norbornadiene (NBD), yielded long sought-after cationic bis(phosphine) cobalt complexes, [(R,R)-(iPrDuPhos)Co(η2,η2-diene)][BArF4]. The COD complex proved substitutionally labile undergoing diene substitution with tetrahydrofuran, NBD, or arenes. The resulting 18-electron, cationic cobalt(I) arene complexes, as well as the [(R,R)-(iPrDuPhos)Co(diene)][BArF4] derivatives, proved to be highly active and enantioselective precatalysts for asymmetric alkene hydrogenation. A cobalt–substrate complex, [(R,R)-(iPrDuPhos)Co(MAA)][BArF4] (MAA=methyl 2-acetamidoacrylate) was crystallographically characterized as the opposite diastereomer to that expected for productive hydrogenation demonstrating a Curtin–Hammett kinetic regime similar to rhodium catalysis.",

keywords = "alkene hydrogenation, asymmetric catalysis, catalyst–substrate complex, cobalt",

author = "Hongyu Zhong and Friedfeld, \{Max R.\} and Chirik, \{Paul J.\}",

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AU - Zhong, Hongyu

AU - Friedfeld, Max R.

AU - Chirik, Paul J.

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N2 - Chloride abstraction from [(R,R)-(iPrDuPhos)Co(μ-Cl)]2 with NaBArF4 (BArF4=B[(3,5-(CF3)2)C6H3]4) in the presence of dienes, such as 1,5-cyclooctadiene (COD) or norbornadiene (NBD), yielded long sought-after cationic bis(phosphine) cobalt complexes, [(R,R)-(iPrDuPhos)Co(η2,η2-diene)][BArF4]. The COD complex proved substitutionally labile undergoing diene substitution with tetrahydrofuran, NBD, or arenes. The resulting 18-electron, cationic cobalt(I) arene complexes, as well as the [(R,R)-(iPrDuPhos)Co(diene)][BArF4] derivatives, proved to be highly active and enantioselective precatalysts for asymmetric alkene hydrogenation. A cobalt–substrate complex, [(R,R)-(iPrDuPhos)Co(MAA)][BArF4] (MAA=methyl 2-acetamidoacrylate) was crystallographically characterized as the opposite diastereomer to that expected for productive hydrogenation demonstrating a Curtin–Hammett kinetic regime similar to rhodium catalysis.

AB - Chloride abstraction from [(R,R)-(iPrDuPhos)Co(μ-Cl)]2 with NaBArF4 (BArF4=B[(3,5-(CF3)2)C6H3]4) in the presence of dienes, such as 1,5-cyclooctadiene (COD) or norbornadiene (NBD), yielded long sought-after cationic bis(phosphine) cobalt complexes, [(R,R)-(iPrDuPhos)Co(η2,η2-diene)][BArF4]. The COD complex proved substitutionally labile undergoing diene substitution with tetrahydrofuran, NBD, or arenes. The resulting 18-electron, cationic cobalt(I) arene complexes, as well as the [(R,R)-(iPrDuPhos)Co(diene)][BArF4] derivatives, proved to be highly active and enantioselective precatalysts for asymmetric alkene hydrogenation. A cobalt–substrate complex, [(R,R)-(iPrDuPhos)Co(MAA)][BArF4] (MAA=methyl 2-acetamidoacrylate) was crystallographically characterized as the opposite diastereomer to that expected for productive hydrogenation demonstrating a Curtin–Hammett kinetic regime similar to rhodium catalysis.

KW - alkene hydrogenation

KW - asymmetric catalysis

KW - catalyst–substrate complex

KW - cobalt

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Syntheses and Catalytic Hydrogenation Performance of Cationic Bis(phosphine) Cobalt(I) Diene and Arene Compounds

Abstract

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