Homolytic H2 cleavage by a mercury-bridged Ni(i) pincer complex [{(PNP)Ni}2{μ-Hg}]

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Abstract

The Hg-bridged (PNP)Ni-complex acts as a synthon for Ni( i) and homolytically cleaves H ₂ to yield [(PNP)NiH].

Abstract

Reduction of the pincer nickel( ii) complex [(PNP)NiBr] with sodium amalgam (Na/Hg) forms the mercury-bridged dimer [{(PNP)Ni} ₂{μ-Hg}], which homolytically cleaves dihydrogen to form [(PNP)NiH]. Reversible CO ₂ insertion into the Ni–H bond is observed for [(PNP)NiH], forming the monodentate κ ¹O-formate complex [(PNP)NiOC(O)H].

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Most cited references 42

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Cyclometalated phosphine-based pincer complexes: mechanistic insight in catalysis, coordination, and bond activation.

Milko E van der Boom, David Milstein, Saumen Chakraborty (2003)

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Metal-ligand cooperation by aromatization-dearomatization: a new paradigm in bond activation and "green" catalysis.

Chidambaram Gunanathan, David Milstein (2011)

In view of global concerns regarding the environment and sustainable energy resources, there is a strong need for the discovery of new, green catalytic reactions. For this purpose, fresh approaches to catalytic design are desirable. In recent years, complexes based on "cooperating" ligands have exhibited remarkable catalytic activity. These ligands cooperate with the metal center by undergoing reversible structural changes in the processes of substrate activation and product formation. We have discovered a new mode of metal-ligand cooperation, involving aromatization-dearomatization of ligands. Pincer-type ligands based on pyridine or acridine exhibit such cooperation, leading to unusual bond activation processes and to novel, environmentally benign catalysis. Bond activation takes place with no formal change in the metal oxidation state, and so far the activation of H-H, C-H (sp(2) and sp(3)), O-H, and N-H bonds has been demonstrated. Using this approach, we have demonstrated a unique water splitting process, which involves consecutive thermal liberation of H(2) and light-induced liberation of O(2), using no sacrificial reagents, promoted by a pyridine-based pincer ruthenium complex. An acridine pincer complex displays unique "long-range" metal-ligand cooperation in the activation of H(2) and in reaction with ammonia. In this Account, we begin by providing an overview of the metal-ligand cooperation based on aromatization-dearomatization processes. We then describe a range of novel catalytic reactions that we developed guided by these new modes of metal-ligand cooperation. These reactions include the following: (1) acceptorless dehydrogenation of secondary alcohols to ketones, (2) acceptorless dehydrogenative coupling of alcohols to esters, (3) acylation of secondary alcohols by esters with dihydrogen liberation, (4) direct coupling of alcohols and amines to form amides and polyamides with liberation of dihydrogen, (5) coupling of esters and amines to form amides with H(2) liberation, (6) selective synthesis of imines from alcohols and amines, (6) facile catalytic hydrogenolysis of esters to alcohols, (7) hydrogenolysis of amides to alcohols and amines, (8) hydrogenation of ketones to secondary alcohols under mild hydrogen pressures, (9) direct conversion of alcohols to acetals and dihydrogen, and (10) selective synthesis of primary amines directly from alcohols and ammonia. These reactions are efficient, proceed under neutral conditions, and produce no waste, the only byproduct being molecular hydrogen and/or water, providing a foundation for new, highly atom economical, green synthetic processes. © 2011 American Chemical Society

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An Efficient Nickel Catalyst for the Reduction of Carbon Dioxide with a Borane

Sumit Chakraborty, Hairong Guan, Jeanette Krause … (2010)

Nickel hydride with a diphosphinite-based ligand catalyzes the highly efficient reduction of CO(2) with catecholborane, and the hydrolysis of the resulting methoxyboryl species produces CH(3)OH in good yield. The mechanism involves a nickel formate, formaldehyde, and a nickel methoxide as different reduced stages for CO(2). The reaction may also be catalyzed by an air-stable nickel formate.

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Author and article information

Journal

Journal ID (publisher-id): CHCOFS

Title: Chemical Communications

Abbreviated Title: Chem. Commun.

Publisher: Royal Society of Chemistry (RSC)

ISSN (Print): 1359-7345

ISSN (Electronic): 1364-548X

Publication date Created: 2015

Publication date (Print): 2015

Volume: 51

Issue: 14

Pages: 2946-2949

Article

DOI: 10.1039/C4CC09743B

SO-VID: 49f847d2-0771-44c8-8cb7-4ad7494ee1a5

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