Abstract
The reaction of various ylides of general formula RCO··[graphic omitted] [R = Ph or m- or p-MeC6H4; X = N or CH; Y = pyridine, NMe3, or PPh3(most work has been carried out with PhCO··[graphic omitted]H5C5= L)] with halide salts of palladium(II), platinum(II), rhodium(III), and iridium(III) affords products containing metallated betaines. Spectroscopic data (i.r., 1H, and 13C n.m.r.) show unambiguously that the aryl group R has become metallated in a position ortho to the carbonyl group and also that the ylide is bidentate (L′)via the group X. There is good evidence to indicate that the mechanism of the reaction involves preliminary co-ordination of the ylide followed by intramolecular electrophilic attack by the metal. Palladium tends to give di-µ-halogeno-complexes, [{Pd(L′)Y}2], whereas in the case of platinum it is possible to prepare [PtL′2] which has cis-Pt–C bonds. Rhodium affords ionic complexes, cis-[RhL′2(H2O)2]Z (Z = Cl, Br, I, or BPh4), which with 2,2′-bipyridyl give [RhL′2(bipy)]Cl. Iridium gives a non-ionic derivative, [IrL′2(H2O)Cl],3H2O. Reactions of the complexes with Ph3P or Bun3P give new complexes containing phosphine oxide such as [PdL′{P(O)Ph3}]Cl, [PtL′{P(O)Ph3}Cl], [RhL′2{P(O)-Bun3}Cl], and [IrL′2{P(O)Ph3}Cl]. The Pd–Cl and Pt–Cl bonds are trans to nitrogen when L = PhCO··[graphic omitted]H5C5. Carbon monoxide reacts reversibly with palladium and iridium complexes of PhCO··[graphic omitted]H5C5to give [PdL′(CO)Cl] and [IrL′2(CO)2]Cl. I.r. evidence suggests CO to be cis to the Pd–C bond in the palladium complex and other observations suggest that the mode of formation is not simple.
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