Magnetic phase transitions in transition-metal complexes with triazole derivatives

Three divalent transition-metal (Co, Ni and Cu) complexes with the organic anion, 1,2,4-triazolato (tr), as a ligand molecule were prepared by means of hydrothermal syntheses and their magnetic properties were investigated by SQUID magnetometry. The Co(tr)₂ and Cu(tr)₂ complexes exhibit long range ordering below 8 and 30 K, respectively, while the Ni(tr)₂ complex does not show any magnetic phase transition down to 1.8 K. The magnetization isotherms of Co(tr)₂ and Cu(tr)₂ measured at 2.0 K show hysteresis loops with the coercive fields of 0.5 and 4.7 kOe, respectively. At temperatures higher than about 50 K, the temperature dependence of the magnetic susceptibility of Co(tr)₂, Ni(tr)₂ and Cu(tr)₂ follows the Curie-Weiss law with the Curie constants of 2.95, 0.945 and 0.420 emu K mol⁻¹ and the Weiss temperatures of −62, −74 and −97 K, respectively. These results suggest that the magnetically ordered phases observed in Co(tr)₂ and Cu(tr)₂ at low temperatures come from antiferromagnetic interactions resulting in canted arrangements of magnetic moments of the transition-metal cations. We discuss here the magnetic interactions in these transition-metal complexes by referring the results of the magnetization measurements.     

5-[4-(1-Hydroxyethyl)phenyl]-10,15,20-triphenylporphyrin as a probe of the transition-state conformation in hydrolase-catalyzed enantioselective transesterifications

5-[4-(1-Hydroxyethyl)phenyl]-10,15,20-triphenylporphyrin (1a) and zinc porphyrin 1b were designed and synthesized to experimentally examine the validity of the transition-state model previously proposed for the lipase-catalyzed kinetic resolution of secondary alcohols. The lipases from Pseudomonas cepacia (lipase PS), Candida antarctica (CHIRAZYME L-2), Rhizomucor miehei (CHIRAZYME L-9), and Pseudomonas aeruginosa (lipase LIP) exhibited excellent enantioselectivity (E >100 at 30 degrees C). Subtilisin Carlsberg from Bacillus licheniformis (ChiroCLEC-BL) also showed high enantioselectivity for 1a (E = 140 at 30 degrees C), and the thermodynamic parameters were determined: DeltaDeltaH = -6.8 +/- 0.8 kcal mol(-1), DeltaDeltaS = -13 +/- 3 cal mol(-1) K(-1). Lipases and subtilisin showed R- and S-preference for 1, respectively. The mechanisms underlying the experimental observations are explained in terms of the transition-state models. The large secondary alcohol 1 is a powerful tool for investigating the conformation of the transition state of the enzyme-catalyzed reactions. The fact that 1 was resolved with high enantioselectivity strongly suggests that the gauche conformation, but not the anti conformation, is taken in the transition state, in agreement with the transition-state models involving the stereoelectronic effect.     

Discontinuous pressure effect upon enantiodifferentiating photosensitized isomerization of cyclooctene

A hydrostatic pressure of up to 750 MPa induced discontinuous changes in the enantiomeric excess of the (E)-isomer obtained in the enantio-differentiating photoisomerization of (Z)-cyclooctene and (Z,Z)-cycloocta-1,5-diene, sensitized by chiral benzene-1,2,4,5-tetracarboxylates; indicating a switching of the enantio-differentiation mechanism, which is attributable to dramatic conformational changes of chiral alkoxycarbonyl auxiliaries at a specific pressure.