De Martino A | PubMed Health

PubMed2000

Random bond XXZ chains with modulated couplings

The magnetization behavior of q-periodic antiferromagnetic spin- 1/2 Heisenberg chains under uniform magnetic fields is investigated in a background of disorder exchange distributions. By means of both real space decimation procedures and numerical diagonalizations in XX chains, it is found that for binary disorder the magnetization exhibits wide plateaus at values of 1+2(p-1)/q, where p is the disorder strength. In contrast, no spin gaps are observed in the presence of continuous exchange distributions. We also study the magnetic susceptibility at low magnetic fields.

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PubMed2000

Stereoselectivity and chiral recognition in copper(I) olefin complexes with a chiral diamine

Trigonal copper(I) complexes of the chiral bidentate ligand (1S,2S)-N,N'-Bis-(mesitylmethyl)-1,2-diphenyl-1,2-ethanediamine ((S,S)-1) have been prepared with hydrocarbon olefins, as well as with allylic alcohols and ethers. The stereochemistry of the complexes has been investigated by 1H NMR spectroscopy and by combined quantum mechanics and molecular mechanics (QM/MM) computational methods. The coordinated chiral nitrogen atoms can display equal (R, R) or opposite (R, S) configuration, the latter being disfavored if steric hindrance is present above and below the coordination plane. Although the complexes exist as rapidly equilibrated mixtures of stereoisomers, one of these is often dominant, and prochiral olefins are coordinated with high enantioface selection. In addition, the [(S,S)-1]-Cu+ fragment selectively recognizes the R enantiomer of secondary allylic alcohols and ethers, as confirmed by the X-ray crystal structure analysis of the adduct with (R)-1-buten-3-ol. The reasons for the observed selectivities have been elucidated, and lead to some implications which are consistent with the enantioselection observed in catalytic cyclopropanation reactions promoted by copper complexes of the same ligand.

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