- Co-ordination chemistry of a P,O-donor ligand: synthesis of new complexes of Ru, Rh and Ir containing Ph2PNHP(O)Ph2 or -
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Methylation of the monooxide Ph2PNHP(O)Ph2 (HL) with MeI in tetrahydrofuran afforded 2H>I which contains a symmetrical hydrogen bond, whereas benzylation with PhCH2Br gave Br.The compound HL can be complexed, as a monodentate P-bound ligand, to various metal centres (RuII, RuIV, RhIII and IrIII).These compounds are excellent precursors for the construction of new five-membered metallacycles containing either M-P-N(H)-P-O or M-P-N-P-O rings.Treatment of (cod)> (cod = cycloocta-1,5-diene) with an excess of MeI gave the oxidative addition compound (cod)> in which a cis configuration of the iodide and methyl ligands is tentatively assigned.Deprotonation of it with NEt3 gave the known neutral iridium(III) complex (cod)>.All compounds were characterised by a combination of 31P- and 1H NMR spectroscopy, IR spectroscopy and microanalysis.The solid-state structures of 2H>I, Br, (cod)>*0.33CHCl3 and (η6-p-MeC6H4Pri)> have been elucidated by X-ray crystallography.The two complexes contain the P,O-chelating ligand Ph2PNHP(O)Ph2 and - respectively.With the exception of the rhodium complex the P-N-P-O fragments all show ?-electron delocalisation.
- Slawin, Alexandra M. Z.,Smith, Martin B.,Woollins, J. Derek
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p. 4575 - 4582
(2007/10/03)
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