Complexes of iridium(III) and rhodium(III) with metallated and unmetallated dimethyl(1-naphthyl)- and methylphenyl(1-naphthyl)-phosphine
- 1 January 1972
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 20,p. 2219-2225
- https://doi.org/10.1039/dt9720002219
Abstract
Dimethyl(1-naphthyl)phosphine (L) is readily metallated in the 8-(peri-)position by iridium (III), (C10H6PMe2 P–C). Thus iridium trichloride with L in 2-methoxyethanol gives [IrCl2(P–C)L2]. In the presence of a base and alcohol further metallation occurs to give [IrCl(P–C)2L] and then [IrH(P–C)2L], which on pyrolysis gives the trimetallated complex fac-[Ir(P–C)3]. [IrHCl2(cyclo-octa-1,5-diene)]2 reacts with L to give [IrHCl2L3], which with chlorine gives mer-[IrCl3L3]. mer-[IrCl3L3] is converted by boiling 2-methoxyethanol into [IrCl2(P–C)L2] very rapidly. [IrCl(cyclo-octa-1,5-diene)]2 reacts with L to give [IrHCl(P–C)L2], which, in boiling 2-methoxyethanol, is converted to [IrCl(P-C)2L]. The base-promoted metallations are readily reversed by HCl, e.g. [IrCl(P–C)2L] gives [IrCl2(P–C)L2] and [IrHCl(P–C)L2] gives [IrHCl2L3], etc. A few rhodium complexes were also prepared such as [RhCl2(P–C)L2] and [RhClL3]. The configurations of these complexes were determined by 1H and /or 31P n.m.r. spectroscopy. I.r. data are also recorded.Keywords
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