Issue 23, 2017

Enhancements in catalytic reactivity and selectivity of homobimetallic complexes containing heteroditopic ligands

Abstract

Rh(I) and Ir(I) homobimetallic complexes were synthesised using a heteroditopic ligand system on a xanthene scaffold containing a monodentate N-heterocyclic carbene ligand and a bidentate bis(pyrazol-1-yl)methane ligand. The complexes were tested as catalysts for the two-step dihydroalkoxylation and two-step hydroamination/hydrosilylation reactions. This is the first known report of an organometallic group 9 complex, Ir(I) bimetallic complex, 13, to selectively favour the opposite spirocyclisation product from that reported in the literature, 14cvs.14b. The Ir(I) homobimetallic complex catalyses the intramolecular hydroamination reaction of alkynamines efficiently and proved to be a highly active catalyst for promoting the subsequent hydrosilylation of the pyrrolines; completing the hydrosilylation reactions in less than 40 seconds. A chloro-bridged bimetallic species was observed in the solid state, revealing that the COD co-ligands present underwent an oxidation.

Graphical abstract: Enhancements in catalytic reactivity and selectivity of homobimetallic complexes containing heteroditopic ligands

Associated articles

Supplementary files

Article information

Article type
Paper
Submitted
11 Apr 2017
Accepted
18 May 2017
First published
23 May 2017

Dalton Trans., 2017,46, 7457-7466

Enhancements in catalytic reactivity and selectivity of homobimetallic complexes containing heteroditopic ligands

M. R. D. Gatus, R. T. McBurney, M. Bhadbhade and B. A. Messerle, Dalton Trans., 2017, 46, 7457 DOI: 10.1039/C7DT01294B

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