Work

Synthesis and Reactivity of (N2P2)Ni Complexes Stabilized by a Diphosphonite Pyridinophane Ligand

Year: 2021

Type: article

Abstract: A series of (N2P2)Ni II complexes (N2P2 = P,P’-ditertbutyl-2,11-diphosphonito[3.3](2,6)pyridinophane) stabilized by a modified tetradentate pyridinophane ligand containing two phosphonite groups were synthesized and characterized. Cyclic voltammetry (CV) studies revealed the accessibility of the Ni I oxidation state at moderate redox potentials for these Ni II complexes. In situ EPR, low-temperature UV-vis, and electrochemical studies were employed to detect the formation of Ni I species during the reduction of Ni II precursors. Furthermore, the [(N2P2)Ni I (CNtBu)](SbF 6 ) complex was isolated upon reduction of the Ni II precursor with 1 equiv of CoCp 2 , and was characterized by EPR and X-ray photoelectron spectroscopy (XPS). Finally, the (N2P2)Ni II Br 2 complex acts as an efficient catalyst for the Kumada cross-coupling of an aryl halide with an aryl or alkyl Grignard, suggesting that the N2P2 ligand can support the various Ni species involved in the catalytic C-C bond formation reactivity.

Source: Organometallics

DOI: 10.1021/acs.organomet.1c00003

Authors: Kei Fuchigami, Michael B. Watson, Giang N. Tran, Nigam P. Rath, Liviu M. Mirica

Institutions: Washington University in St. Louis, University of Illinois Urbana-Champaign, University of Missouri–St. Louis

Language: English

Topic: Organometallic Complex Synthesis and Catalysis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: U.S. Department of Energy, Basic Energy Sciences

Awards: G3793751952, NEW; NOVEL PALLADIUM CATALYSTS FOR THE OXIDATIVE OLIGOMERIZATION OF METHANE & CARBON DIOXIDE REDUCTION; PI - LIVIU MIRICA