Bru Francis, Lesieur Mathieu, Poater Albert, Slawin Alexandra M Z, Cavallo Luigi, Cazin Catherine S J
Department of Chemistry, Center for Sustainable Chemistry, Ghent University, Krijgslaan 281, 9000, Ghent, Belgium.
EaSTCHEM School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, UK.
Chemistry. 2022 Dec 1;28(67):e202201917. doi: 10.1002/chem.202201917. Epub 2022 Oct 5.
The synthesis and isolation of [Pd(NHC)(PhC≡CPh)] complexes are reported. These new 14-electron Pd(0)-complexes are key synthons leading to known palladium(0) and palladium(II) species, as well as permitting access to unprecedented mixed NHC-phosphite palladium(0) complexes. This motif permits the facile catalytic hydrosilylation of allenes. DFT calculations have allowed the characterization of the relatively weak interaction between the metal and the diphenylacetylene ligand, with a comparison with a series of ligands with more or less coordinating power, bearing varied structural and electronic properties.
报道了[Pd(NHC)(PhC≡CPh)]配合物的合成与分离。这些新型14电子Pd(0)配合物是合成已知钯(0)和钯(II)物种的关键合成子，同时也能用于制备前所未有的NHC-亚磷酸酯钯(0)混合配合物。这种结构使得丙二烯的催化硅氢化反应能够轻松进行。密度泛函理论（DFT）计算有助于表征金属与二苯乙炔配体之间相对较弱的相互作用，并与一系列具有不同配位能力、结构和电子性质各异的配体进行比较。
