Pyrimidine-hydrazone and phosphole architectures have been combined to create a new heteroditopic ligand capable of forming heterobimetallic Zn/Pd, Pb/Pd and Cu/Pd complexes in high yielding stepwise or one pot reactions. The catalytic activity of these complexes in Heck coupling and Miyaura borylation reactions was investigated.
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http://dx.doi.org/10.1039/c7dt04449f | DOI Listing |
Molecules
November 2024
Institut für Chemie und CINSaT, University of Kassel, Heinrich Plett-Straße 40, 34132 Kassel, Germany.
The chemistry of bidentate ligands with a dppf-like motif, where phosphorus is fully or partially replaced by other pnictogens as donor sites, is summarized and discussed in this comprehensive review, while covering the literature from 1966 to 2024, related to more than 165 original references and discussing more than 75 independent chemical entities (-). Besides addressing synthetic, structural, and electrochemical aspects of such compounds, their donor properties and metal coordination behavior is discussed, along with catalytic applications. Based on their electronic and steric situations, trends in the performance of such compounds, either as ligands for catalysis or on their own merits for non-catalytic purposes, have been elucidated.
View Article and Find Full Text PDFInorg Chem
September 2024
Department of Chemistry, Middle Tennessee State University, Murfreesboro, Tennessee 37132, United States.
A new class of rigid, photoactive heteroditopic anionic ligands based on the 1,10-disubstituted [-BH] anion was designed and six of these compounds were obtained from [-BH] in three steps with yields in the range of 25-30%. The design includes two apical substituents, a metal coordinating cyano group and an azinium (4-cyanopyridinium, 4,4'-bipyridinium, pyrazinium, pyrimidinium, and pyridazinium), which provides a secondary binding site. The azinium substituent is involved in an efficient intramolecular charge transfer process and compensates one of the two delocalized negative charges of the boron cluster.
View Article and Find Full Text PDFInorg Chem
May 2024
Department of Chemistry, University of Kansas, 1567 Irving Hill Road, Lawrence, Kansas 66045, United States.
Incorporation of secondary redox-inactive cations into heterobimetallic complexes is an attractive strategy for modulation of metal-centered redox chemistry, but quantification of the consequences of incorporating strongly Lewis acidic trivalent cations has received little attention. Here, a family of seven heterobimetallic complexes that pair a redox-active nickel center with La, Y, Lu, Sr, Ca, K, and Na (in the form of their triflate salts) have been prepared on a heteroditopic ligand platform to understand how chemical behavior varies across the comprehensive series. Structural data from X-ray diffraction analysis demonstrate that the positions adopted by the secondary cations in the crown-ether-like site of the ligand relative to nickel are dependent primarily on the secondary cations' ionic radii and that the triflate counteranions are bound to the cations in all cases.
View Article and Find Full Text PDFInorg Chem
March 2024
Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne (EPFL), Lausanne CH-1015, Switzerland.
Octahedral coordination cages of the general formula [PdL](BF) were obtained by combining [Pd(CHCN)](BF) with heteroditopic N-donor ligands. Four different ligands were employed. These ligands have 3-pyridyl donor groups at one end and 4-pyridyl, imidazolyl, or triazolyl donor groups at the other end.
View Article and Find Full Text PDFInorg Chem
January 2024
College of Chemistry and Environmental Science, Qujing Normal University, Qujing 655011, P. R. China.
In this paper, the synthesis, photophysics, electrochemistry, and intramolecular energy transfer of two series of dinuclear and tetranuclear metallic complexes [(bpy)MM(bpy)] ( = 1, 2; M = Ru, M = Ru/Os; M = Os, M = Ru) and {[Ru(bpy)()]Ru} based on new heteroditopic bridging ligands ( = 6-phenyl-4-Hpip-2-2'-bipyridine, = 6-Hpip-2-2'-bipyridine, Hpip = 2-phenyl-1-imidazo[4,5-][1,10]phenanthroline) are reported. The dimetallic and tetrametallic complexes exhibit rich redox properties with successive reversible metal-centered oxidation and ligand-centered reduction couples. All complexes display intense absorption in the entire ultraviolet-visible spectral regions.
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