X-ray structure and UV spectroscopic studies of (adenmato-N9)triethylphosphinegold(I)

The preparation, characterization, and X-ray structure analysis of (adeninatoN9)triethylphosphinegold(I) is reported. The crystal structure consists of discrete molecules, the adeninate anion coordinates via the N(9) atom with a Au-N(9) bond distance of 2.057(5) Å and the linear geometry about the Au atom is completed by the P atom of a disordered Et₃P ligand; the Au-P(1) bond distance is 2.238(2) Å and the N(9)-Au-P(1) bond angle is 178.8(2)°. The crystals are orthorhombic, space groupPbca, with unit cell dimensionsa=8.528(1),b=17.797(3),c=18.526(2) Å andZ=8. The structure was refined by a full-matrix least-squares procedure to finalR=0.030 andR _w =0.033 for 1749 reflections withI>2.5a(I). The electronic spectrum of the complex dissolved in water in the near ultraviolet is consistent with essentially separate -electron systems of the adenine and phosphinegold moieties; a conclusion which corroborates the X-ray structural results.     

Photochemical expulsion of the neutral monodentate ligand L in Ru(terpy*)(diimine)(L)2+: a dramatic effect of the steric properties of the spectator diimine ligand

A series of photoreactive complexes of the type Ru(terpy*)(N-N)(L)(2+), where terpy* is 4'-(3,5-ditertiobutylphenyl)-2,2':6',2' '-terpyridine, N-N is the bidentate chelate phen or dmp (phen = 1,10-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline), and L is the monodentate ligand dms, MeBN, or MeOBN (dms = dimethyl sulfide, MeBN = 2,6-dimethyl benzonitrile, MeOBN = 2,6-dimethoxybenzonitrile), has been synthesized and fully characterized by proton NMR spectroscopy, electrospray mass spectrometry, and UV-vis spectroscopy. The X-ray structures of four complexes were also obtained. In neat pyridine, the quantum yields for the photosubsitution of L by pyridine were measured and showed dramatic variations depending on the steric interactions between the spectator bidentate ligand and the leaving monodentate ligand L. The use of dmp instead of phen multiplied the photosubstitution efficiency by a factor of 20-50, depending on L. This effect could be qualitatively correlated to the distortions observed in the X-ray structures of the corresponding complexes. The highly distorted structure of Ru(terpy)(dmp)(dms)(PF(6))(2) showed a very high photosubsitution quantum yield phi = 0.36 in neat pyridine. The high photoreactivity of some of the compounds makes them particularly promising as components of future light-driven molecular machines.     

Synthesis of 3-formyltetronic acid and enamine derivatives

The first reported synthesis of 3-formyltetronic acid and its conversion to enamine derivatives is described. 3-Dimethylaminomethylene-2,4-dioxotetrahydrofuran derivatives were also prepared by treatment of tetronic acids with dimethylformamide diethyl acetal. Nmr spectral studies are included.     

The search for a new model structure of β-Factor XIIa

We present the search for a new model of -factor XIIa, a blood coagulation enzyme, with an unknown experimental 3D-structure. We decided to build not one but three different models using different homologous proteins as well as different techniques and different modellers. Additional studies, including extensive molecular dynamics simulations on the solvated state, allowed us to draw several conclusions concerning homology modelling, in general, and -factor XIIa, in particular.     

(1-Adamantanethio)pyridines and tetrahydropyridines from the reaction of 1-adamantanethiol with pyridine I-oxide in acetic anhydride

The reaction of pyridine 1-oxide with 1-adamantanethiol in acetic anhydride produced a mixture of 2- and 3-(1-adamantanethio)pyridines, 1-aeetyl-2-(1-adamantanethio)-3-hydroxy-4-acetoxy-1,2,3,4-telrahydropyridine and the corresponding 3-acetoxyderivative. Pure substances were separated by means of column chromatography on alumina. The tetrahydropyridines were identified by means of their proton magnetic and mass spectra. 4-(1-Adamantanethio)pyridine was synthesized from 4-chloropyridinc and 1-adamantanethiol. The three isomeric (1-adamantanethio)-pyridines were, each, cleaved by concentrated hydrochloric acid to give 1-chloroadamantane and the corresponding pyridinethiol.     

Role of pyridine in the catalytic activation of sodium hypochlorite in the presence of manganese porphyrin

Steric and electronic influences of various substituted pyridines support the hypothesis of the coordination of pyridine in the manganese porphyrin-catalysed epoxidation of olefins with sodium hypochlorite solution.