The value of gold: coordination ambiphilic diphosphanylborane ligands to AuCl provides unusual square-planar gold(I) complexes. Insight is gained on the nature gold→borane interactions in these complexes through natural bond orbital (NBO) analysis and 197Au Mössbauer spectroscopy. seminal formalism MLlXx (M=transition metal, L=2e-donor ligand, X=1e-donor ligand) a unified description for transition-metal Besides well-known L- X-type ligands, ability Lewis acids act as zero-electron...

The ambiphilic triphosphine−borane ligand 1 {TPB = [o-iPr2P-(C6H4)]3B} readily coordinates to all group 10 and 11 metals afford a complete series of metal boratranes (TPB)[M] 2−8 (2: M Ni, 3: Pd, 4: Pt, 5: CuCl, 6: AgCl, 7: AuCl, 8: Au+). Spectroscopic structural characterization unambiguously establishes the presence M→B interactions in these complexes. first evidence for borane coordination copper silver is provided, Au→B interaction shown persist upon chloride abstraction. Experimental...

Symmetry from within: Coordination of a triphosphanyl–borane ligand to gold(I) and platinum(0) affords metallaboratranes exhibiting C3 symmetry both in solution the solid state. Such helical geometry is supported by axial M→B dative interactions results envelope conformations PCCBM metallacycles. Supporting information for this article available on WWW under http://www.wiley-vch.de/contents/jc_2002/2008/z705024_s.pdf or author. Please note: The publisher not responsible content functionality...

Gold gets a grip: Spectroscopic, structural, and computational results provide evidence for unprecedented Au→Si Au→Sn interactions in gold(I) complexes derived from diphosphino-substituted silane stannane ligands (see scheme).

Gallant exchange: Upon coordination of phosphanyl gallane ligands to AuCl, both neutral and zwitterionic complexes coexist. NMR spectroscopy provides direct evidence for the transfer chloride between gold gallium in diphosphanyl gallane. The introduction a third buttress allows separation structural characterization two isomers (see picture; Au yellow, P red, Cl green, Ga blue).

The monophosphino-boranes o-iPr2P(C6H4)BR2 (1: R = Ph and 3: Cy) diphosphino-boranes [o-R2P(C6H4)]2BPh (5: 6: iPr) readily react with CuCl to afford the corresponding complexes {[o-iPr2P(C6H4)BPh2]Cu(μ-Cl)}2 2, {[o-iPr2P(C6H4)BCy2]Cu(μ-Cl)}2 4, {[o-Ph2P(C6H4)]2BPh}CuCl 7, {[o-iPr2P(C6H4)]2BPh}CuCl 8. presence of Cu→B interactions supported by arene coordination within 8 has been unambiguously evidenced NMR spectroscopy X-ray diffraction studies. unique η2-BC mode adopted 7 thoroughly...

Although [Ni(S2CNBui2)2] is stable at high temperatures in a range of solvents, solvothermal decomposition occurs 145 °C oleylamine to give pure NiS nanoparticles, while n-hexylamine 120 mixture Ni3S4 (polydymite) and results. A combined experimental theoretical study gives mechanistic insight into the process can be used account for observed differences. Upon dissolution primary amine, octahedral trans-[Ni(S2CNBui2)2(RNH2)2] result as shown by situ XANES EXAFS confirmed DFT calculations....

Square-planar nickel bis(dithiocarbamate) complexes, [Ni(S2CNR2)2], have been prepared and utilised as single source precursors to nanoparticulate sulfides. While they are stable in the solid-state around 300 °C, heating oleylamine at 230 5 mM solutions afford pure α-NiS, where outcome is independent of substituents. DFT calculations show an electronic effect rather than steric hindrance influences resulting particle size. Decomposition iso-butyl derivative, [Ni(S2CNiBu2)2], has studied...

The triphosphine−indane TPI ([o-i-Pr2P(C6H4)]3In) has been prepared and found to react with [Pd(P-t-Bu3)2] [AuCl(SMe2)]. According X-ray diffraction analyses DFT calculations, the ensuing complexes both display original donor−acceptor M→In interactions, although of markedly different nature magnitude.

Liganden sind Gold wert: Die Koordination von ambiphilen Diphosphanylboran-Liganden an AuCl ergibt ungewöhnliche quadratisch-planare Gold(I)-Komplexe. NBO-Analysen und 197Au-Mößbauer-Spektroskopie geben Aufschluss über die Eigenschaften der Gold→Boran-Wechselwirkung. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2001/2007/z703518_s.pdf or from author. Please note: The publisher not responsible content functionality of any supporting...

Coordination of ambiphilic diphosphine-silane ligands [o-(iPr(2)P)C(6)H(4)](2)Si(R)F (R=F, Ph, Me) to AuCl affords pentacoordinate neutral silicon compounds in which the metal atom acts as a Lewis base. X-ray diffraction analyses, NMR spectroscopy, and DFT calculations substantiate presence Au→Si interactions these complexes, result trigonal-bipyramidal geometries around silicon. The single electron-withdrawing fluorine is sufficient observe coordination silane σ-acceptor ligand, provided it...

Symmetrie kommt von innen: Die Koordination eines Triphosphanylboran-Liganden an Gold(I) und Platin(0) führt zu Metallaboratranen, die sowohl in Lösung als auch im Festkörper C3-Symmetrie aufweisen. helicale Anordnung resultiert aus den gefalteten Konformationen der PCCBM-Metallacyclen wird durch M→B-Donorwechselwirkungen unterstützt.

Abstract Mobiles Chlorid : Die Koordination von Phosphanylgallan‐Liganden an AuCl führt zu neutralen und zwitterionischen Komplexen, die im Gleichgewicht vorliegen. NMR‐spektroskopische Studien belegen Chloridübertragung zwischen dem Goldatom Galliumatom des Liganden. Nach Einführung eines dritten Phosphanylarms lassen sich beiden Koordinationsisomere trennen strukturell charakterisieren (siehe Bild; Au gelb, P rot, Cl grün, Ga blau). magnified image

We present computational studies of CO2 sorption in two different classes ionic liquid. The addition carbon dioxide to four superbase liquids, [P3333][Benzim], [P3333][124Triz], [P3333][123Triz] and [P3333][Bentriz], was studied using the DFT approach considering anions alone individual ion pairs. anion clearly resulted formation a covalently-bound carbamate function with strength binding correlated experimental capacity. In pair however cation significantly alters nature bonding such that...

Gold findet Halt: Spektroskopische, strukturchemische und computergestützte Studien liefern Belege für neuartige Au→Si- Au→Sn-Wechselwirkungen in Gold(I)-Komplexen, die mit diphosphanylsubstituierten Silan- bzw. Stannanliganden erhalten wurden (siehe Schema). Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted by the authors. Please note: The publisher is...

Coordination of the triphosphine–fluorosilane [o-(iPr2P)C6H4]3SiF to AuCl results in formation a trigonal pyramidal cationic complex. Though cationic, gold center acts as Lewis base and is engaged significant Au→Si interaction, substantiated by X-ray diffraction NMR spectroscopy. In solution, P,P,P,Si tetracoordinate complex coexists with neutral P,P,Cl tricoordinate form, pendant phosphine buttress without interaction. The bonding situation two isomeric forms has been assessed DFT...

The experimental design of improved nanocatalysts is usually based on shape control and surface-ligand dependent. First-principle calculations can guide their design, both in terms activity selectivity, provided that theoretical descriptors be defined used a prescreening process. As consequence the Sabatier principle Brønsted–Evans–Polanyi relationship, an important prerequisite before optimizing catalytic properties nanoparticles knowledge selective adsorption strengths reactants at...

The addition of carbon dioxide to four superbase ionic liquids, [P3333][Benzim], [P3333][124Triz], [P3333][123Triz] and [P3333][Bentriz] was studied using a molecular DFT approach involving anions alone individual ion pairs. Intermolecular bonding within the pairs is characterised by number weak hydrogen bonds, with anion geometrically arranged so as maximize interactions between heterocyclic N atoms cation. pairing energies show no correlation observed CO2 adsorption capacity. Addition...

New values are reported for the Gibbs energies of formation from elements hydrocerussite Pb(OH) 2 •(PbCO 3 ) and hydrozincite [Zn(OH) ] •(ZnCO .These ⌬ 0 G f were obtained electrochemical cells without liquid junction.We determined3 Ϯ 4 kJ/mol hydrozincite.These results allow future cell experiments to be performed determine other hydroxycarbonate minerals using either Pb amalgam-hydrocerussite or Zn amalgam-hydrozincite as reference electrodes.These electrodes provide a strategy...

The hydrophosphination reaction of 1,3-butadiene in the presence Cp(2)EuH has been studied by DFT methods. It possible to show that such a can be catalytically performed and active species is Cp(2)EuPH(2). phosphido complex formed from hydride either one step (direct P-H activation Cp(2)EuH) or two-step (1,3-butadiene insertion into Eu-H bond followed activation). latter calculated preferred pathway. catalytic cycle predicted efficient since virtually no side reactions occur. Three...