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Issue 10, 2011
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Synthesis and reactivity of half-sandwich (η5-C5Me5)Ir(iii) complexes of a cyclometallated aryl phosphine ligand

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Abstract

Reaction of the Ir(III) dimer [(η5-C5Me5)IrCl2]2 with PMeXyl2 (Xyl = 2,6-C6H3Me2), in the presence of the poorly coordinating base 2,2,6,6-tetramethyl piperidine, gives a chloride complex 1-Cl, resulting from hydrogen chloride elimination involving one of the phosphine benzylic hydrogen atoms and concomitant cyclometallation. Related compounds containing other halide or pseudohalide ligands, 1-Br, 1-Cl, 1-SCN, can be made, the latter featuring S-coordination of the ambidentate thiocyanate to the soft Ir(III) Lewis acid centre, as suggested by IR data and demonstrated by X-ray crystallography. Hydride 2-H, and alkyl derivatives 3 (Me) and 4 (CH2SiMe3) can also be prepared from 1-Cl and appropriate hydride and alkylating reagents. An interesting H/D exchange chemistry that occurs in the presence of CD3OD has been disclosed for 1-Cl, 1-Br and 2-H. For the halide derivatives, deuterium incorporation takes place into the methylene and methyl sites of their cyclometallated ligand, whereas for 2-H only the hydride and methylene (Ir–CH2) protons participate in the exchange, which is strikingly accelerated by catalytic amounts of acids.

Graphical abstract: Synthesis and reactivity of half-sandwich (η5-C5Me5)Ir(iii) complexes of a cyclometallated aryl phosphine ligand

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Supplementary files

Article information


Submitted
15 Mar 2011
Accepted
05 May 2011
First published
02 Jun 2011

New J. Chem., 2011,35, 2122-2129
Article type
Paper

Synthesis and reactivity of half-sandwich (η5-C5Me5)Ir(III) complexes of a cyclometallated aryl phosphine ligand

J. Campos, E. Álvarez and E. Carmona, New J. Chem., 2011, 35, 2122
DOI: 10.1039/C1NJ20244H

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