Issue 13, 2019

Simple and reactive Ir(i) N-heterocyclic carbene complexes for alkyne activation

Abstract

Two simple unsymmetrical monometallic Ir(I) complexes with an N-heterocyclic carbene ligand and an analogous bimetallic Ir(I) complex were synthesised. These complexes were found to be extremely active catalysts for a range of C–X (X = N or O) and Si–N bond forming reactions involving alkyne and imine activation for dihydroalkoxylation, hydroamination and hydrosilylation reactions. These catalysts exhibited reaction rates far exceeding those of other Rh(I) and Ir(I) complexes previously reported. In addition, a small change to the ligand design (phenyl vs. mesityl) substantially affected both the reactivity and product selectivity of the catalyst. The Ir(I) complex bearing a mesitylene wingtip provided unprecedented regioselectivity in the dihydroalkoxylation reaction and a new kinetic product from the typical hydrosilylation protocol of 2-benyzlpyrroline to produce an N-silylaminoalkene. Our mechanistic studies indicated that this transformation proceeded via a dehydrogenative coupling mechanism.

Graphical abstract: Simple and reactive Ir(i) N-heterocyclic carbene complexes for alkyne activation

Supplementary files

Article information

Article type
Paper
Submitted
23 Jan 2019
Accepted
26 Feb 2019
First published
28 Feb 2019

Dalton Trans., 2019,48, 4333-4340

Simple and reactive Ir(I) N-heterocyclic carbene complexes for alkyne activation

M. R. D. Gatus, I. Pernik, J. A. Tompsett, S. C. Binding, M. B. Peterson and B. A. Messerle, Dalton Trans., 2019, 48, 4333 DOI: 10.1039/C9DT00313D

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