Terminal, 4-coordinate phosphinidenes of Ta supported by bulky anilide ligands are prepared by an apparent reaction sequence involving metallaziridine phosphanide complexes.
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A metal and a metalloid Lewis acid bridged by a μ-phosphinidene.
Dalton Trans
June 2024
Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Str.1, 53121 Bonn, Germany.
Dinuclear phosphinidene complexes bridging two transition metal centres are now well established. However, a phosphinidene bridging a metal centre and a main group Lewis acid has not yet been reported. Herein, we describe the generation of a highly reactive phosphinidene complex bridging a tungsten and a boron centre.
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Acc Chem Res
December 2023
Spin-X Institute, School of Chemistry and Chemical Engineering, State Key Laboratory of Luminescent Materials and Devices, Guangdong-Hong Kong-Macao Joint Laboratory of Optoelectronic and Magnetic Functional Materials, South China University of Technology, Guangzhou 510641, P. R. China.
ConspectusAs phosphorus analogues of alkylidene (or carbene) and imido (or nitrene) complexes, phosphinidene complexes have received great attention not only for their fundamental scientific merits but also for their ability to build new phosphorus-containing molecules. A large number of phosphinidene complexes in bridging, mononuclear, or terminal coordination modes have been synthesized, and their reactivity has been extensively explored. However, the synthesis of rare-earth metal (scandium, yttrium, and lanthanide metal) phosphinidene complexes lagged behind the transition metal and actinide congeners for decades.
View Article and Find Full Text PDFE-H Bond Cleavage Processes in Reactions of Heterometallic Phosphinidene-Bridged MoRe and MoMn Complexes with Hydrogen and p-Block Element Hydrides.
Organometallics
October 2023
Departamento de Química Orgánica e Inorgánica/IUQOEM, Universidad de Oviedo, E-33071 Oviedo, Spain.
Reactions of complexes [MoMCp(μ-PMes*)(CO)] with H and several p-block element (E) hydrides mostly resulted in the cleavage of E-H bonds under mild conditions [M = Re () and Mn (); Mes* = 2,4,6-CHBu]. The reaction with H (ca. 4 atm) proceeded even at 295 K to give the hydrides [MoMCp(μ-H)(μ-PHMes*)(CO)].
View Article and Find Full Text PDFChallenging an old paradigm by demonstrating transition metal-like chemistry at a neutral nonmetal center.
Nat Commun
October 2023
Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Str. 1, 53121, Bonn, Germany.
We describe nonmetal adducts of the phosphorus center of terminal phosphinidene complexes using classical C- and N-ligands from metal coordination chemistry. The nature of the L-P bond has been analyzed by various theoretical methods including a refined method on the variation of the Laplacian of electron density ∇ρ along the L-P bond path. Studies on thermal stability reveal stark differences between N-ligands such as N-methyl imidazole and C-ligands such as tert-butyl isocyanide, including ligand exchange reactions and a surprising formation of white phosphorus.
View Article and Find Full Text PDFCycloaddition and C-S Bond Cleavage Processes in Reactions of Heterometallic Phosphinidene-Bridged MoRe and MoMn Complexes with Alkynes and Phenyl Isothiocyanate.
Organometallics
August 2023
Departamento de Química Orgánica e Inorgánica/IUQOEM, Universidad de Oviedo, E-33071 Oviedo, Spain.
Reactions of [MoReCp(μ-PMes*)(CO)] with internal alkynes RC≡CR yielded the phosphapropenylidene-bridged complexes [MoReCp(μ-κ:η-PMes*CRCR)(CO)] (Mes* = 2,4,6-CHBu; R = COMe, Ph). Terminal alkynes HC≡CR gave mixtures of isomers [MoReCp(μ-κ:η-PMes*CHCR)(CO)] and [MoReCp(μ-κ:η-PMes*CRCH)(CO)], with the first isomer being major (R = COMe) or unique (R = Bu), indicating the relevance of steric repulsions during the [2 + 2] cycloaddition step between Mo=P and C≡C bonds in these reactions. Similar reactions were observed for [MoMnCp(μ-PMes*)(CO)].
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