From diarylruthenium complexes to ortho-metallated ketones: a mechanistic and crystal structure study

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Abstract
In the presence of CHCl3, CCl4, or Etl, diary1 complexes [Ru(CO)2(C6H4Y-4)(C6H4Y′-4)L2](Y = Y′= Me, L = PMe2Ph or AsMe2Ph; Y = Y′= Cl, L = PMe2Ph; Y = Me, Y′= Cl, L = PMe2Ph) are converted in solution into products [R[graphic omitted])C6H4Y}XL2], where X = Cl or I. The structure of [R[graphic omitted])C6H4Me}Cl(PMe2Ph)2], complex (3a), has been determined by X-ray crystallography. The proposed mechanism involves a two-step combination of aryl and carbonyl ligands to give [Ru(CO){OC(C6H4Y-4)(C6H4Y′–4)}L2], followed by insertion of the metal into a C–H bond in one of the arene rings and reaction of the resulting hydrido-complex with the halogen-containing compound. Probably as a result of the stereochemistry of the insertion step, the product [R[graphic omitted])C6H4Y}XL2] is initially obtained as an isomer with mutually cis L ligands; this then rearranges to the isolated product with trans L ligands. The iodide ligand in the complex [R[graphic omitted])C6H4Me}I(PMe2Ph)2] can be displaced by Me3CNC, and the complete organic ligand in complex (3a) is transferred from ruthenium to mercury on treatment with HgCl2.

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