Search results for "rhodium"
showing 10 items of 244 documents
Voltammetric determinations of platinum and rhodium in particulate of Palermo (Italy) area
2012
Traffic has an important impact on the air quality which affects both the environmental and human health. Since the introduction of PGE-containing catalytic converters, a number studies have been undertaken to determine the effects of PGE emissions on human and to environment. This requires the development of good analytic methods to measure Pt and Rh concentrations in environmental matrices, as well to estimate background concentrations. In this paper are presented the results concerning Pt and Rh concentrations in PM10 samples collected at five stations within the urban area of Palermo. The highest mean values (Pt= 13 pg/m3, Rh=9.8 pg/m3) were recorded at an urban station, and the lowest …
Easy preparation of Cp*-functionalized N-heterocyclic carbenes and their coordination to rhodium and iridium
2010
A simple high-yielding method for the preparation of a tetramethylcyclopentadienyl-NHC ligand is described. This ligand has been successfully coordinated to Rh and Ir. A related Cp*-NHC ligand with a -CH(2)CMePh- linker between the Cp* and the NHC is also described, together with its coordination to Rh and Ir. This latter ligand, affords the orthocyclometallation of the phenyl ring yielding a constrained structure in which the ligand is tridentate. All the complexes have been fully characterized and their crystal structures are described. Preliminary catalytic results on the beta-alkylation of secondary alcohols and N-alkylation of aniline with primary alcohols are also reported.
Synthesis, reactivity, crystal structures and catalytic activity of new chelating bisimidazolium-carbene complexes of Rh
2003
A series of new bridging, chelating and pincer N-heterocyclic carbenes of RhI and RhIII have been obtained under mild conditions. The compounds have been fully characterised and their crystal structures determined. The chelate-pincer coordination of the ligands means that the stability of these compounds is significantly greater than other carbene complexes of Rh. The compounds have been tested in catalytic reactions such as hydrogen transfer from alcohols to ketones, and hydrosilylation of terminal olefins and alkynes; they show a high activity for both processes. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
A New Rhodium(III) Complex with a Tripodal Bis(imidazolylidene) Ligand. Synthesis and Catalytic Properties
2003
A new bis(imidazolylidene) tripodal ligand has been obtained by a simple method. The coordination of this ligand to Rh provides the first Rh(III) complex with a bis(carbene) ligand in a tripodal coordination, and its catalytic properties toward hydrogen transfer have been examined.
Vergleichende dimerisierung der enantiomere von Oct-1-in-3-ol mit chiralen rhodium-phosphan-komplexen
1996
Abstract Three optically active phosphanes ([(S)-2-methylbutyl]3−nP[phenyl]n(n = 0, 1, 2), were tested as ligands in rhodium(I) complexes to form catalysts for the enantioselective dimerisation of (R)- and (S)-oct-1-yn-3-ol. The catalytic reaction provides enantioselectivity for this type of CC bond formation. For reactions at 45–75°C and depending on the P-ligand used the rates vary for both enantiomers from 6:1 to 50:1 in favour of the (S)-octynol.
Synthesis, Coordination to Rh(I), and Hydroformylation Catalysis of New β-Aminophosphines Bearing a Dangling Nitrogen Group: An Unusual Inversion of…
2002
Variants of the beta-aminophosphine L(1) [Ph(2)PCH(2)CH(Ph)NHPh] containing additional nitrogen donor functions have been prepared. These functions are branched off the C atom adjacent to the P atom, or the P atom itself. Ligand [Ph(2)PCH(o-C(6)H(4)NMe(2))CH(Ph)NHPh] has been obtained as a mixture of two diastereomers L(3A) and L(3B) by lithiation of L(2) [Ph(2)PCH(2)(o-C(6)H(4)NMe(2))] with n-BuLi followed by PhCH=NPh addition and hydrolysis. The diastereomers have been separated by fractional crystallization from ethanol. Ligand Et(2)NCH(2)P(Ph)CH(2)CH(Ph)NHPh has been obtained as a mixture of two diastereomers L(5A) and L(5B)(starting with P-Ph reductive cleavage of L(1) by lithium and s…
[(1R,4S)-(+)-3-Benzoyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-olato-κ2 O 2,O 3](η4-norbornadiene)rhodium(I)
2010
In the title complex mol-ecule, [Rh(C(17)H(19)O(2))(C(7)H(8))], the rhodium(I) metal centre is coordinated by the O atoms of a benzoyl-camphorate anion and the C=C bonds of the norbornadiene mol-ecule into a slightly distorted square-planar coordination geometry. The six-membered chelate ring is essentially planar (r.m.s. deviation = 0.0378 Å) and forms a dihedral angle of 31.67 (11)° with the phenyl ring.
Modular P-Chirogenic Aminophosphane-Phosphinite Ligands for Rh-Catalyzed Asymmetric Hydrogenation: A New Model for Prediction of Enantioselectivity
2007
An original series of P-chirogenic aminophosphane-phosphinite (AMPP) ligands has been synthesized from (+)- or(–)-ephedrine in 23 to 61 % overall yields by a versatile three-step methodology. The AMPP ligands, bearing either one or two P-chirogenic centers, were used in the form of rhodium complexes for the catalyzed hydrogenation of α-acetamidocinnamate as a test reaction. Notably, even with AMPP ligands all derived from (+)-ephedrine, variation of the substituent on a P-center allowed the phenylalanine derivatives to be obtained in either (S) or (R) absolute configurations, with ee values ranging from 99 % (S) to 88 % (R). The asymmetric induction was analyzed with the aid of X-ray struct…
Cyclodextrines confinantes : synthèse, propriétés complexantes et utilisation en catalyse asymétrique
2014
This manuscript is concerned with the design of novel catalytic systems derived from metallocyclodextrins. The first part describes new ways of functionalising the cyclodextrin primary face regioselectively for accessing inherently chiral P,P’ chelators. These heterodentate ligands gavequantitatively cis-chelate complexes with various d8 cations. Their rhodium(I) complexes were assessed in the asymmetric hydrogenation and hydroformylation of prochiral olefins. Thecoordination and catalytic properties of two phosphines derived from a- and b-cyclodextrin are also reported. With their phosphorus lone pair pointing toward the CD core, these confining ligands force the coordinated metal centre t…
Die oligomerisierung endständiger hydroxyacetylene mit rhodiumkomplexkatalysatoren
1982
The substrate and ligand influence on oligomerisation of terminal hydroxyacetylenes catalysed by rhodium complexes has been studied. In this reaction α- and β-hydroxyacetylenes were compared with each other and with an unsubstituted terminal alkyne. The concentration dependant ligand control with Ph3As and Ph3P has been compared and different ligand association behaviour is found, because only with Ph3As as ligand at intermediate concentrations cyclic trimers are selectively formed. Some brief experiments with different p- and o-substituted triphenylarsines show electronic and marked steric influences on the oligomerisation of 3-methylbutyne-1-ol-3.