| Abstract
| - The selective ortho mercuration of tricarbonylchromium derivatives of 2-phenylpyridine,N,N-dimethylbenzylamine, (1S)-1-(dimethylamino)-1-phenylethane, and 2-phenyl-2-oxazolineby Hg(OAc)2 is reported. The mercurations of the latter (η6-arene)Cr(CO)3 complexes bearingan endogenous ligand have been carried out in soft conditions with yields ranging from 13to 83%. The optically active complex of (1S)-1-(dimethylamino)-1-phenylethane was stereoselectively orthomercurated. The conversion of the chloromercurated complexes, e.g. (η6-Ar-HgX)Cr(CO)3, into the corresponding homoleptic trinuclear [(η6-Ar)Cr(CO)3]2Hg complexeswas readily carried out by reaction with Me4NCl in boiling acetone. In almost all cases, theso-called symmetrization reaction afforded a mixture of two diastereomers, except for thederivative of (1S)-1-(dimethylamino)-1-phenylethane, which afforded a unique “symmetrized”product. This result suggests that the “symmetrization” reaction occurred with retention ofthe configuration of the mercury-bound ipso carbon atom. The trimetallic and bimetallicmercurated (η6-arene)Cr(CO)3 complexes were readily converted into cyclopalladated binuclear complexes upon transmetalation with Pd(II) salts. The structures of two ortho-mercurated compounds and two ortho-palladated complexes are reported.
- The syntheses of mercurated (η6-arene)tricarbonylchromium complexes by reaction with Hg(OAc)2 and their subsequent conversions into novel cyclopalladated compounds are reported.
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