Structural investigation of high-valent manganese-salen complexes by UV/Vis, Raman, XANES, and EXAFS spectroscopy.

XANES and EXAFS spectroscopic studies at the Mn-K- and Br-K-edge of reaction products of (S,S)-(+)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminomanganese(III) chloride ([(salen)Mn(III)Cl], 1) and (S,S)-(+)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminomanganese(III) bromide ([(salen)Mn(III)Br], 2) with 4-phenylpyridine N-oxide (4-PPNO) and 3-chloroperoxybenzoic acid (MCPBA) are reported. The reaction of the Mn(III) complexes with two equivalents of 4-PPNO leads to a hexacoordinated compound, in which the manganese atom is octahedrally coordinated by four oxygen/nitrogen atoms of the salen ligand at an average distance of approximately 1.90 A and two additional, axially bonded oxygen atoms of the 4-PPNO at 2.

Catalyzed Asymmetric Arylation Reactions.

Addition and substitution reactions with carbon nucleophiles are fundamental processes in organic synthesis, and the development of general catalytic asymmetric variants thereof is still a major challenge today. In contrast to enantioselective alkyl transfer reactions, the corresponding arylations have not yet reached a high level of maturity. The existing protocols are either of no general applicability or are limited in terms of selectivity.

Application of a Planar Chiral η -Cyclopentadienylrhenium(I)tricarbonyl Complex in Asymmetric Catalysis: Highly Enantioselective Phenyl Transfer to Aldehydes.

A novel planar chiral cyrhetrene 1 has been identified as an efficient catalyst precursor for the asymmetric synthesis of diarylmethanol compounds 2 by phenylation of aldehydes. Compared to the corresponding ferrocene derivative, the performance of the cyrhetrene is superior or at least equally as good and gives excellent enantioselectivities even with catalyst loadings as low as 2 mol %.