Fast substitution of chloride for bromide and iodide trans to triphenylsilyl in trans-PtCl(SiPh3)(PMe2Ph)2 has been studied by stopped-flow spectrophotometry in acetonitrile solution. Substitution is reversible with an observable solvent path via the solvento complex trans-[Pt(SiPh3)(MeCN)(PMe2Ph)2]+, which has also been synthesized and characterized in solution. Rate constants for the forward and

Ligand exchange at square-planar [Pd(MeCN)4]2+ and [Pd(EtCN)4]2+ has been studied by 1H NMR line broadening and at [Pt(MeCN)4]2+ and [Pt(EtCN)4]2+ by isotopic labelling using 1H NMR spectroscopy in deuteriated nitromethane. Exchange takes place via two-term rate laws Rex/4 = (k1 + k2[RCN])cM with well defined k1 paths. Rate constants per co-ordination site k1298/s–1, k2298/kg mol–1 s–1 are 6.9 ± 1Ligand exchange at square-planar [Pd(MeCN)4]2+ and [Pd(EtCN)4]2+ has been studied by 1H NMR line broadening and at [Pt(MeCN)4]2+ and [Pt(EtCN)4]2+ by isotopic labelling using 1H NMR spectroscopy in deuteriated nitromethane. Exchange takes place via two-term rate laws Rex/4 = (k1 + k2[RCN])cM with well defined k1 paths. Rate constants per co-ordination site k1298/s–1, k2298/kg mol–1 s–1 are 6.9 ± 1

The kinetics and mechanism of the reactions between trans-[PtI3(PPh3)]– and trans-[PtI3(SbPh3)]– with pyridine, 2- and 4-methylpyridine in acetonitrile solvent have been studied by stopped-flow spectrophotometry. The crystal and molecular structures of the tetrabutylammonium salts of the two anions have been determined. Substitution of iodide trans to stibine is reversible and takes place via paraThe kinetics and mechanism of the reactions between trans-[PtI3(PPh3)]– and trans-[PtI3(SbPh3)]– with pyridine, 2- and 4-methylpyridine in acetonitrile solvent have been studied by stopped-flow spectrophotometry. The crystal and molecular structures of the tetrabutylammonium salts of the two anions have been determined. Substitution of iodide trans to stibine is reversible and takes place via para

SynopsisProtonolysis of the title compounds involves rate-determining proton transfer to the substrate. Subsequent isomerization is dissociative. Activation volumes for the two processes have opposite signs. A new kinetic β-hydrogen accelerating effect for isomerization favoring the fluxionality of a T-shaped 14-electron intermediate is reported.AbstractAbstract ImageProtonolysis of the complexes SynopsisProtonolysis of the title compounds involves rate-determining proton transfer to the substrate. Subsequent isomerization is dissociative. Activation volumes for the two processes have opposite signs. A new kinetic β-hydrogen accelerating effect for isomerization favoring the fluxionality of a T-shaped 14-electron intermediate is reported.AbstractProtonolysis of the complexes cis-[PtR2(PEt3

Heckscher published in 1915 a book on the economics of World War I in Swedish. He analyzed the costs and the finances of war along similar lines as his contemporary Pigou (1916). Heckscher reached farther by making a distinction between the short and the long-run costs of war. He also provided a comprehensive theoretical and empirical analysis of the sources of funds for war finance, including a pHeckscher published in 1915 a book on the economics of World War I in Swedish. He analyzed the costs and the finances of war along similar lines as his contemporary Pigou (1916). Heckscher reached farther by making a distinction between the short and the long-run costs of war. He also provided a comprehensive theoretical and empirical analysis of the sources of funds for war finance, including a p

Eighty-two alcoholics were offered a 2-year out-patient programme characterized by stressing the patients' own decisions both in joining the programme and in the choice of objectives and methods, by repeated feedbacks through treatment evaluations, and by relapse prevention. The 58 patients who accepted were more often married than the others. All but eight completed the programme. The most import

The present review reports on the influence of alcohol drinking and alcohol use disorders on psychiatric disorders and suicidal behaviour. The base of the study was previous reviews of the National Institute on Alcohol Abuse and Alcoholism publication Alcohol and Health in 1993 and by Helgason in 1996. Using a defined search strategy in Medline, another 42 articles from 1994 to 1996 were included