Cationic complexes of iridium. Part I. The preparation and properties of some phosphine and arsine complexes
- 1 January 1970
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc. A
- p. 2909-2914
- https://doi.org/10.1039/j19700002909
Abstract
A series of cationic five-co-ordinate complexes of formula [Ir(CO)3L2]BPh4(I)(L = tertiary phosphine or arsine) have been prepared by passage of carbon monoxide through solutions of trans-[IrCl(CO)L2] in the presence of sodium tetraphenylborate. From these, the corresponding cationic dihydride complexes [IrH2(CO)2L2]BPh4(II) have been obtained by reaction with hydrogen under mild conditions. Some of the complexes (I) lose carbon monoxide reversibly to give stable four-co-ordinate complexes of formula [Ir(CO)2L2]BPh4(III). Addition of MeO2C·C⋮C·CO2Me (A) to (I) acetylene complexes of formula [Ir(A)(CO)2L2]BPh4. The hydride complex (II)(where L = PMePh2) reacts with π-bonding ligands L′(L′= CO, tertiary phosphines, phosphites, etc.) to give complexes of formula [Ir(CO)2(PMePh2)2L′]BPh4 which, for L′= PMePh2, reacts further with hydrogen to give [IrH2(CO)(PMePh2)3]BPh4. Reaction of trans-[IrCl(CO)(PMePh2)2] with tertiary phosphites, L′, in the presence of NaBPh4 gives complexes of formula [Ir(CO)(PMePh2)2L′2]BPh4. The i.r. and 1H n.m.r. spectra of the new complexes prepared are reported, and are used in making stereochemical assignments.Keywords
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