Dual Utility of a Single Diphosphine-ruthenium Complex: a Precursor for New Complexes And, a Pre-catalyst for Transfer-hydrogenation and Oppenauer Oxidation

Overview

Journal RSC Adv

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2022 Apr 28

PMID 35481203

Authors

Aparajita Mukherjee

Samaresh Bhattacharya

Affiliations

Soon will be listed here.

Abstract

The diphosphine-ruthenium complex, [Ru(dppbz)(CO)Cl] (dppbz = 1,2-bis(diphenylphosphino)benzene), where the two carbonyls are mutually and the two chlorides are , has been found to serve as an efficient precursor for the synthesis of new complexes. In [Ru(dppbz)(CO)Cl] one of the two carbonyls undergoes facile displacement by neutral monodentate ligands (L) to afford complexes of the type [Ru(dppbz)(CO)(L)Cl] (L = acetonitrile, 4-picoline and dimethyl sulfoxide). Both the carbonyls in [Ru(dppbz)(CO)Cl] are displaced on reaction with another equivalent of dppbz to afford [Ru(dppbz)Cl]. The two carbonyls and the two chlorides in [Ru(dppbz)(CO)Cl] could be displaced together by chelating mono-anionic bidentate ligands, anions derived from 8-hydroxyquinoline (Hq) and 2-picolinic acid (Hpic) loss of a proton, to afford the mixed-tris complexes [Ru(dppbz)(q)] and [Ru(dppbz)(pic)], respectively. The molecular structures of four selected complexes, [Ru(dppbz)(CO)(dmso)Cl], [Ru(dppbz)Cl], [Ru(dppbz)(q)] and [Ru(dppbz)(pic)], have been determined by X-ray crystallography. In dichloromethane solution, all the complexes show intense absorptions in the visible and ultraviolet regions. Cyclic voltammetry on the complexes shows redox responses within 0.71 to -1.24 V SCE. [Ru(dppbz)(CO)Cl] has been found to serve as an excellent pre-catalyst for catalytic transfer-hydrogenation and Oppenauer oxidation.

Citing Articles

Ruthenium complexes of 1,4-diazabutadiene ligands with a -RuCl moiety for catalytic acceptorless dehydrogenation of alcohols: DFT evidence of chemically non-innocent ligand participation.

Mukherjee A, Datta S, Richmond M, Bhattacharya S RSC Adv. 2023; 13(36):25660-25672.

PMID: 37649575 PMC: 10463240. DOI: 10.1039/d3ra04750d.

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