Chelating and bridging diphosphinoamine (PPh2)(2)N(Pr-i) complexes of copper(I)

The ligand bis(diphenylphosphino) isopropylamine (dppipa) has been shown to be a versatile ligand sporting different coordination modes and geometries dictated by copper(I). Most of the molecular structures were confirmed by X-ray crystallography. It is found in a chelating mode, in a monomeric complex when the ligand to copper ratio is 2:1. A tetrameric complex is formed when low ratios of ligand to metal (1: 2) were used. But with increasing ratios of ligand to metal (1: 1 and 2: 1), a trimer or a dimer was obtained depending on the crystallization conditions. Variable temperature P-31{H-1} NMR spectra of these complexes in solution showed that the Cu-P bond was labile and the highly strained 4-membered structure chelate found in the solid state readily converted to a bridged structures. On the other hand, complexes with the ligand in a bridging mode in the solid state did not form chelated structures in solution. The effect of adding tetra-alkylammonium salts to solutions of various complexes of dppipa were probed by P-31{H-1} NMR and revealed the effect of counter ions on the stability of complexes in solution. (C) 2008 Elsevier B.V. All rights reserved.

Am unexpected entry into the silver(I) chemistry of diphosphazane ligands: Crystal and molecular structures of [Ag{Ph2PN(Pr-i)PPh2}(CF3SO3)](2), [Ag{Ph2PN(Pr-i)PPh(OC6H3Me2-2,6)}(2)]PF6, and [Ag-3(mu-Cl)(2){Ph2PN(R)PPh2}(3)]PF6 (R = H, Pr-i)

Mononuclear, binuclear and trinuclear silver(l) complexes were obtained unexpectedly while probing the reactivity of diphosphazane ligands of the type X2PN(Pr-i)PXY towards the ruthenium-based precursor Ru(bipy)(2)Cl-2 center dot 2H(2)O, in the presence of a silver salt as a chloride scavenger. Subsequently, the reactions of AgX [X = Cl, NO3 or CF3SO3] with Ph2PN(R)PPh(Y) [R = H, Y = Ph; R = Pr-i, Y = Ph or OC6H3Me2-2,6] in a 1: 1 or 1:2 molar ratio have been investigated. Mononuclear or binuclear Ag(I) complexes containing either chelating or bridging diphosphazane ligands are obtained. Trinuclear silver(l) complexes are accessible by the treatment of diphosphazane ligands, Ph2PN(R)PPh2 [R = H, Pr-i] with AgCl using piperidine as the solvent. In the presence of a suitable chloride donor species, the mononuclear and binuclear complexes of Ph2PN(Pr-i)PPh2 are transformed slowly to the trinuclear complex [Ag-3(mu-Cl)(2){Ph2PN(Pr-i)PPh2}(3)]X, over a period 20 h. The structures of representative complexes have been confirmed by X-ray crystallography and the salient structural features are discussed

Organometallic chemistry of diphosphazanes .13. Palladium complexes of unsymmetrical diphosphazanes Ph(2)PN(Pr-i)PYY'

Unsymmetrical diphosphazanes Ph(2)PN(Pr-i)PYY' [YY' = O2C12H8 (L(1)), O2C20H12 (L(2)); Y = Ph and Y' = OC6H4Br-4 (L(3)), OC(6)H(4)Me-4 (L(4)), OC(6)H(3)Me(2)-3,5 (L(5)), N(2)C(3)HMe(2)-3,5 (L(6))] react with cis-[PdCl2(COD)] (COD = cycloocta-1,5-diene) giving the chelate complexes of the type cis-[PdCl2{eta(2)-Ph(2)PN(Pr-i)PYY'}] [YY' = O2C12H8 (1), O2C20H12 (2), Y = Ph and Y' = OC6H4Br-4 (3), OC(6)H(4)Me-4 (4), OC(6)H(3)Me(2)-3,5 (5), N(2)C(3)HMe(2)-3,5 (6)]. The P-N bond in 3 and 5 undergoes a facile cleavage in methanol solution to give cis-[PdCl2{eta(1)Ph(2)P(OMe)}{eta(1)-PhP(NHPri)(Y')}] [Y' = OC6H4Br-4 (7), OC(6)H(3)Me(2)-3,5 (8)]. Reactions of Pd-2(dba)(3) . CHCl3 (dba = dibenzylideneacetone) with the diphosphazanes Ph(2)PN(Pr-i)PPhY' [Y' = OC(6)H(4)Me-4 (L(4)), N(2)C(3)HMe(2)-3,5 (L(6)), N2C3H3 (L(7))] in the presence of MeI yields cis-[PdI2{eta(2)-Ph(2)PN(Pr-i)PPhMe}] (9); the P-O or P-N(pyrazolyl) bond of the starting ligands is cleaved and a p-C(Me) bond is formed. An analogous oxidative addition reaction in the presence of Ph(2)PN(Pr-i)PPh(2) (L(8)) yields cis-[PdI(Me)(eta(2)-L(8))] (10) and cis-[PdI2(eta 2-L(8))] (11). The structures of 8 and 9 have been determined by X-ray diffraction. Copyright (C) 1996 Elsevier Science Ltd

Ciência e Universidade na I República

A reforma do ensino superior que se seguiu à implantação da I República impôs modificações estruturais na conjuntura científica nacional. O Estado republicano incumbiu então as universidades e os estabelecimentos de ensino superior da promoção da investigação científica, reconhecendo-lhes um papel central na modernização da ciência nacional. Promoveu um processo de concentração, sob tutela universitária, de vários estabelecimentos científicos autónomos e de modernização dos gabinetes e dos laboratórios de ensino universitários. Estas medidas permitiram o arranque da investigação científica moderna, prática que progressivamente se complexificaria, quer a nível institucional, quer humano, exigindo mudanças importantes no sector, nomeadamente pela organização de um instituto autónomo de coordenação da actividade científica. Neste sentido pretende-se analisar o processo de institucionalização da investigação científica na universidade, tendo em consideração os métodos de reprodução e especialização, os ritmos específicos do seu desenvolvimento, os espaços e os actores e as várias interdependências com as conjunturas política, económica, social e cultural.

As bibliotecas na I República : do discurso político à visão dos intelectuais

Este trabalho visa contribuir para uma melhor compreensão da problemática das bibliotecas públicas durante o período da I República (1910-1926). Pretende-se, assim, apreender à luz do ideário educativo republicano, qual foi a visão doutrinária e as propostas para a criação e/ou reorganização das bibliotecas públicas apresentadas por parte do poder político e de distintos eruditos que pensaram e escreveram sobre esta temática. Neste sentido, a análise documental privilegiou como fontes principais, os diplomas legais considerados mais significativos e estruturantes para o sector bibliotecário, promulgados pelos governos republicanos, bem como os textos doutrinários versados em artigos e ensaios escritos por Raul Proença, António de Bettencourt Ataíde e António Ferrão, os quais deram um importante contributo para a dinamização desta área. O trabalho está organizado em três capítulos: no primeiro, procedemos a uma breve abordagem do contexto político e histórico que favoreceu o desenvolvimento das bibliotecas públicas; no segundo, centramo-nos na análise de legislação referente às bibliotecas Eruditas, Populares e Móveis e, no terceiro, procuramos sinalizar as principais temáticas que mobilizaram os autores acima referidos em torno das Bibliotecas. As bibliotecas públicas, nas suas diferentes tipologias, deveriam constituir-se como espaços complementares à escola, ao serviço da instrução e da cultura, facilitando o acesso ao livro, ao saber, à informação e ao conhecimento e, deste modo, contribuírem para elevar o nível de Educação de todos os cidadãos.

Věstník Královské české společnosti náuk. Třída mathematicko-přírodovědecká = Sitzungsberichte der Königl. Böhmischen Gesellschaft der Wissenschaften. Mathematisch-naturwissenschaftliche Classe.

1896, pt. 2

Dodatek k ruskému přízvuku /

Mode of access: Internet.

Česká přísloví; sbírka přísloví, průpovědí a pořekadel lidu českého v Čechách, na Moravě a v Slezsku. Díl I: Přísloví staročeská.

pt. 1. A-N.--pt. 2. O-Z.

Zavisimostʹ "Revizora" Gogoli︠a︡ otʺ komedīi Kvitki "Prīi︠e︡zzhīĭ izʺ stolit︠s︡y" /

Includes bibliographical references.

Věstník Královské české společnosti náuk. Třída mathematicko-přírodovědecká.

Královská Česká společnost náuk, Prague. Třída mathematicko-přirodovědecka. Sitzungberichte.

La femme, le conte de fées , la 1er. République au Portugal : Ana de Castro Osório

Ana de Castro Osório, ao escrever Uma Lição da História (1909), traduz os saber, sentir e fazer literários segundo a sensibilidade feminina, à luz da vontade de consolidar a consciência nacional (sobremodo da mulher portuguesa nascida aristocrata ou burguesa). Ao analisar a narrativa, reflecte-se no presente artigo, sobre a alegoria como estratégia literária mais adequada para promover pela instrução nacional a implantação da república - objectivo tão imperioso quanto o momento económico e político, carente de acção reformadora, assim o exigia, sem dispensar quer a aristocracia, quer a burguesia

Catalytic cyclopropanation of olefins using copper(I) diphosphinoamines

Catalytic cyclopropanation reactions of olefins with ethyl diazoacetate were carried out using copper(I) diphosphinoamine (PPh2)(2)N(R) (R = Pr-i, H, Ph and -CH2-C6H4-CH=CH2) complexes at 40 degrees C in chloroform. High yields of the cyclopropanes were obtained in all cases. The rate of the reaction was influenced by the nuclearity of the complex and the binding mode of the ligand which was either bridging or chelating. Comparison of isostructural complexes shows that the rate follows the order R = Pr-i > H > Ph, where R is the substituent on the N. However, cyclopropane formation versus dimerization of the carbene, and trans to cis ratios of cyclopropane was similar in all cases. The nearly identical selectivity for different products formed was indicative of a common catalytic intermediate. A labile "copper-olefin" complex which does not involve the phosphine or the counterion is the most likely candidate. The differences in the reaction rates for different complexes are attributed to differences in the concentration of the catalytically active species which are in equilibrium with the catalytically inactive copper-phosphinoamine complex. To test the hypothesis a diphosphinoamine polymer complexed to copper(I) was used as a heterogeneous catalyst. Leaching of copper(I) and deactivation of the catalyst confirmed the proposed mechanism. (C) 2008 Elsevier B. V. All rights reserved.

Synthesis, crystal structures and spectroscopic properties of copper(I) complexes containing beta-dialdiminato supporting ligands

Two mononuclear neutral copper(I) complexes, Cu(L-1)PPh3 (1), Cu(L-2)(PPh3)(2) (2) ([L-1](-) = [{N((C6H3Pr2)-Pr-i-2,6)C(H)}(2)CPh](-); [L-2](-) = [{N(C6H5)C(H)}(2)CPh](-)) have been synthesized and structurally characterized by X-ray crystallography. In complex 1, the copper(I) atom is in a distorted three-coordinate trigonal planar environment, whereas in complex 2 with the less sterically hindered beta-dialdiminato ligand, the copper(I) atom is the centre of a four-coordinate distorted tetrahedron. At room temperature complexes 1 and 2 in a film of PMMA exhibit green emission at 543 and 549 nm with lifetimes of 5.28 and 5.32 ns, respectively.