Ni(I)-Alkyl Complexes Bearing Phenanthroline Ligands: Experimental Evidence for CO2 Insertion at Ni(I) Centers

Rosie J Somerville; Carlota Odena; Marc F Obst; Nilay Hazari; Kathrin H Hopmann; Ruben Martin

doi:10.1021/jacs.0c04695

Ni(I)-Alkyl Complexes Bearing Phenanthroline Ligands: Experimental Evidence for CO₂ Insertion at Ni(I) Centers

J Am Chem Soc. 2020 Jun 24;142(25):10936-10941. doi: 10.1021/jacs.0c04695. Epub 2020 Jun 12.

Authors

Rosie J Somerville^{1

2}, Carlota Odena^{1

2}, Marc F Obst³, Nilay Hazari⁴, Kathrin H Hopmann³, Ruben Martin^{1

5}

Affiliations

¹ Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain.
² Departament de Quı́mica Analı́tica i Quı́mica Orgànica, Universitat Rovira i Virgili, c/Marcel·lı́ Domingo 1, 43007 Tarragona, Spain.
³ Hylleraas Center for Quantum Molecular Sciences, Department of Chemistry, UiT The Arctic University of Norway, N-9307 Tromsø, Norway.
⁴ Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520, United States.
⁵ ICREA, Passeig Lluı́s Companys 23, 08010 Barcelona, Spain.

Abstract

Although the catalytic carboxylation of unactivated alkyl electrophiles has reached remarkable levels of sophistication, the intermediacy of (phenanthroline)Ni(I)-alkyl species-complexes proposed in numerous Ni-catalyzed reductive cross-coupling reactions-has been subject to speculation. Herein we report the synthesis of such elusive (phenanthroline)Ni(I) species and their reactivity with CO₂, allowing us to address a long-standing question related to Ni-catalyzed carboxylation reactions.

Publication types

Research Support, N.I.H., Extramural
Research Support, Non-U.S. Gov't

MeSH terms

Carbon Dioxide / chemistry*
Carboxylic Acids / chemical synthesis
Catalysis
Coordination Complexes / chemical synthesis
Coordination Complexes / chemistry*
Ligands
Nickel / chemistry*
Phenanthrolines / chemical synthesis
Phenanthrolines / chemistry*

Substances

Carboxylic Acids
Coordination Complexes
Ligands
Phenanthrolines
Carbon Dioxide
Nickel

Grants and funding

R01 GM120162/GM/NIGMS NIH HHS/United States