The synthesis and structures of new 16-electron disilene palladium complexes with 2,6-dimethylphenyl isocyanide and phenyldimethylphosphine ligands [L(1)L(2)Pd{(t-BuMe(2)Si)(2)Si=Si(SiMe(2)Bu-t)(2)}, where L(1) = L(2) = PhMe(2)P; L(1) = (cyclohexyl)(3)P, L(2) = 2,6-dimethylphenyl isocyanide; L(1) = L(2) = 2,6-dimethylphenyl isocyanide] are described. Comparison of the X-ray structural parameters around the disilene moiety among these complexes and related bis(trimethylphosphine)(disilene)palladium and 14-electron (tricyclohexylphosphine)(disilene)palladium revealed that the pi-complex character is sensitive to the residual ligands and increases with decreasing the strength of sigma-donation from the ligands.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1039/b512414j | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Oxidation-Induced Detachment of Ruthenoarene Units and Oxygen Insertion in Bis-Pd(II) Hexaphyrin π-Ruthenium Complexes.
Molecules
June 2020
Department of Chemistry, Graduate School of Science, Kyoto University, Kyoto 606-8502, Japan.
Two types of new bis-Pd(II) hexaphyrin π-ruthenium complexes are reported. A double-decker bis-Pd(II) hexaphyrin π-ruthenium complex was obtained by oxidation-induced detachment of a ruthenoarene unit from the triple-decker complex and oxygen-inserted triple-decker bis-Pd(II) hexaphyrin π-ruthenium complex was obtained upon treatment of bis-Pd(II) [26]hexaphyrin with [RuCl(-cymene)] under aerobic conditions. Although π-metal complexation of porphyrinoids often results in decreased global aromaticity due to the enhancement of local 6π aromatic segments, distinct aromatic characters were indicated for and by H-NMR spectral and theoretical calculations.
View Article and Find Full Text PDFUnderstanding the Origin of Phosphorescence in Bismoles: A Synthetic and Computational Study.
Inorg Chem
July 2018
Department of Chemistry , University of Alberta, 11227 Saskatchewan Drive , Edmonton , Alberta T6G 2G2 , Canada.
A series of bismuth heterocycles, termed bismoles, were synthesized via the efficient metallacycle transfer (Bi/Zr exchange) involving readily accessible zirconacycles. The luminescence properties of three structurally distinct bismoles were explored in detail via time-integrated and time-resolved photoluminescence spectroscopy using ultrafast laser excitation. Moreover, time-dependent density functional theory computations were used to interpret the nature of fluorescence versus phosphorescence in these bismuth-containing heterocycles and to guide the future preparation of luminescent materials containing heavy inorganic elements.
View Article and Find Full Text PDFPrecursor States of Organic Adsorbates on Semiconductor Surfaces are Chemisorbed and Immobile.
Chemphyschem
January 2017
Faculty of Chemistry and Material Sciences Centre, Philipps-Universität Marburg, Hans-Meerwein-Str. 4, 35032, Marburg, Germany.
Intermediate states to covalent attachment of molecules on surfaces, so called precursors, are usually considered to be physisorbed and mobile. We show that this view should be reconsidered and provide evidence for a chemisorbed precursor for ethylene on Si(001). The character of the molecule-surface bond as a π complex is determined and quantified using our recently developed method for energy and charge analysis in extended systems.
View Article and Find Full Text PDFThe pentamethylcyclopentadienylsilicon(II) cation: synthesis, characterization, and reactivity.
Chemistry
July 2014
Faculty of Chemistry, University of Bielefeld, 33615 Bielefeld (Germany).
In the flourishing chemistry of divalent silicon, π-complex formation between silicon and the pentamethylcyclopentadienyl (Cp*) group is one of the successful strategies for thermodynamic and/or kinetic stabilization. Here, the diverse reactivity of the [Cp*Si](+) ion is described. Its chemistry is characterized by the addition of anionic and neutral nucleophiles and by the easy hapticity change and the leaving-group character of the Cp* group.
View Article and Find Full Text PDFBonding and structure of disilenes and related unsaturated group-14 element compounds.
Proc Jpn Acad Ser B Phys Biol Sci
October 2012
Department of Chemistry, Graduate School of Science, Tohoku University, Sendai, Japan.
Structure and properties of silicon-silicon doubly bonded compounds (disilenes) are shown to be remarkably different from those of alkenes. X-Ray structural analysis of a series of acyclic tetrakis(trialkylsilyl)disilenes has shown that the geometry of these disilenes is quite flexible, and planar, twist or trans-bent depending on the bulkiness and shape of the trialkylsilyl substituents. Thermal and photochemical interconversion between a cyclotetrasilene and the corresponding bicyclo[1.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!