A platinum-beryllium adduct (see structure) was prepared by the reaction of [Pt(PCy(3))(2)] and BeCl(2). Treatment with methyllithium resulted in ligand substitution at the beryllium center. Both complexes were structurally characterized and display unprecedented two-center two-electron bonds between a transition metal and beryllium.
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http://dx.doi.org/10.1002/anie.200900521 | DOI Listing |
J Am Chem Soc
January 2025
Instituto de Investigaciones Químicas (IIQ), Departamento de Química Inorgánica and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad de Sevilla and Consejo Superior de Investigaciones Científicas (CSIC). Avenida Américo Vespucio 49, 41092 Sevilla, Spain.
Bimetallic complexes have demonstrated a great ability to enhance the activity of monometallic systems for bond activation and catalysis. In this work, we explore the opposite approach: using a second metal to passivate the activity of another by reversible bimetallic inhibition. To do so we have synthesized a family of nine electrophilic gold complexes of formula Au(PR)(NTf) ([NTf] = [N(SOCF)]) that can act as inhibitors in the semihydrogenation of terminal and internal alkynes catalyzed by the iconic iridium Vaska complex IrCl(CO)(PPh).
View Article and Find Full Text PDFJ Mol Model
December 2024
Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387, Krakow, Poland.
Context: The interpretation of ETS-NOCV for typical covalent and dative-covalent chemical bonds is presented and compared with that for halogen bonds. Possible tuning of the strength of halogen bonding is considered, first by applying an electric field (modeled by the point charges or the electric field vector), and then by constructing a model transition-metal complex with enhanced strength of halogen bonding. For all the systems, the ETS-NOCV picture is supplemented by the analysis of the deformation in molecular electrostatic potential (ΔMEP).
View Article and Find Full Text PDFMolecules
October 2024
Department of Molecular Chemistry and Materials Science, Weizmann Institute of Science, Rehovot 7610001, Israel.
In our recent work, we revisited C-H and C-C bond activation in rhodium (I) complexes of pincer ligands PCP, PCN, PCO, POCOP, and SCS. Our findings indicated that an η-CCH agostic intermediate acts as a common precursor to both C-C and C-H bond activation in these systems. We explore the electronic structure and bonding nature of these precleavage complexes using electron density and molecular orbital analyses.
View Article and Find Full Text PDFActa Crystallogr C Struct Chem
November 2024
Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM, km 14.5 Carretera Toluca-Atlacomulco, Toluca 50200, Mexico.
Chempluschem
September 2024
College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang, 471934, China.
The N→C dative bond (DB), intramolecular chalcogen bond and π conjugation play important roles in determining the structures and properties of some molecular carbon materials and organic/polymeric photovoltaic materials. In this work, the interplay between the N→C DB, intramolecular chalcogen bond and π conjugation in the complexes formed by cyclo[18]carbon and C polyyne with 1,2,5-chalcogenadiazoles has been investigated in detail by using reliable quantum chemical calculations. This study has made four main findings.
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