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Issue 12, 2015
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Synthesis and structure of a new phosphonium-1-indenylide (PHIN) ligand, 4,7-dimethyl-1-C9H4PMePh2, and of new PHIN complexes of rhodium and iridium

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Abstract

This paper describes the synthesis, properties and crystal structure of a new phosphonium-1-indenylide ligand, 4,7-dimethyl-1-C9H4PMePh2, and the syntheses of complexes of rhodium(I) and iridium(I) containing both the parent PHIN ligand, 1-C9H6PMePh2 (I) and 4,7-dimethyl-1-C9H4PMePh2 (II). The complexes [M(η4-COD)(η5-PHIN)]X (M = Rh, Ir; PHIN = I, II; COD = 1,5-cyclooctadiene; X = Cl, BF4) and [Rh(η5-I)(PPh3)2]BF4 have been prepared and characterized by HR-ESM, elemental analyses and NMR spectroscopy. While [Ir(η4-COD)(η5-I)]Cl undergoes one or more chloride-induced exchange processes involving the COD ligand, the analogous complexes of rhodium and iridium with the more weakly coordinating BF4 counter anion exhibit no exchange processes. In contrast, [Rh(η5-I)(PPh3)2]BF4 undergoes an exchange process involving the inequivalent PPh3 phosphorus atoms and which is rationalized using DFT calculations.

Graphical abstract: Synthesis and structure of a new phosphonium-1-indenylide (PHIN) ligand, 4,7-dimethyl-1-C9H4PMePh2, and of new PHIN complexes of rhodium and iridium

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Supplementary files

Article information


Submitted
06 Jul 2015
Accepted
24 Sep 2015
First published
05 Oct 2015

New J. Chem., 2015,39, 9429-9441
Article type
Paper

Synthesis and structure of a new phosphonium-1-indenylide (PHIN) ligand, 4,7-dimethyl-1-C9H4PMePh2, and of new PHIN complexes of rhodium and iridium

K. Purdavaie, M. C. Baird and P. H. M. Budzelaar, New J. Chem., 2015, 39, 9429
DOI: 10.1039/C5NJ01756D

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