Oxidative addition of dialkylphosphites to complexes of iridium(I) and rhodium(I) |
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| Authors: | MA Bennett TRB Mitchell |
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| Institution: | Research School of Chemistry, Australian National University, P.O. Box 4, Canberra, A.C.T. 2600 Australia;Department of Chemistry, Queen''s University, Belfast, BT9 5AG, N. Ireland Great Britain |
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| Abstract: | The PH bond of dialkylphosphites (dimethylphosphite, 5,5-dimethyl-1,3-dioxa-2-phosphorinane and 4,4,5,5-tetramethyl-1,3-dioxa-2-phospholane) oxidatively adds to irClL2(L = PPh3, AsPh3) and IrCl(PMe2Ph)3 generated in situ to give six-coordinate hydrido(dialkylphosphonato)iridium(III) complexes, e.g. IrHClL2{(MeO)2-PO}2H] and IrHCl(PMe2Ph)3PO(OMe)2]. Addition of triphenylphosphine to a solution containing IrCl(C8H14)2]2 and dimethylphosphite in a 1:2 mol ratio gives a five-coordinate hydrido (dimethylphosphonato)iridium(III) complex IrHCl(PPh3)2{PO(OMe)2}, from which six-coordinate pyridine and acetylacetonato complexes IrHCl(PPh3)2(C5H5N){PO(OMe)2} and IrH(PPh3)2(acac){PO(OMe)2} can be obtained. The ligand arrangements in the various complexes are inferred from IR, 1H and 31P NMR data. |
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