0000000001178634
AUTHOR
Christine Caputo
Phospha-Fischer Carbenes: Synthesis, Structure, Bonding, and Reactions of Pd(0)− and Pt(0)−Phosphenium Complexes
The analogy between cationic group 10 metal−phosphenium complexes and Fischer carbenes has been formalized through structural and reactivity studies and by energy decomposition analysis (EDA) of the M−P bond. The studied compounds were the three-coordinate, 16-electron species [(NHPMes)M(PPh3)2]OTf (M = Pt (1) and Pd (2); [NHPMes]+ is the N-heterocyclic phosphenium (NHP) cation, [tiebar above startPN(2,4,6-Me3-C6H2)CH2CH2tiebar above endN(2,4,6-Me3-C6H2)]+, OTf = trifluoromethanesulfonate); these were made by reaction of [NHPMes]OTf with M(PPh3)4. The metal−phosphenium bond in both compounds was dominated by metal-to-ligand π-donation. This differed from the M−C bonds in the analogous N-het…
Counterintuitive Mechanisms of the Addition of Hydrogen and Simple Olefins to Heavy Group 13 Alkene Analogues
The mechanism of the reaction of olefins and hydrogen with dimetallenes ArMMAr (Ar = aromatic group; M = Al or Ga) was studied by density functional theory calculations and experimental methods. The digallenes, for which the most experimental data are available, are extensively dissociated to gallanediyl monomers, :GaAr, in hydrocarbon solution, but the calculations and experimental data showed also that they react with simple olefins, such as ethylene, as intact ArGaGaAr dimers via stepwise [2 + 2 + 2] cycloadditions due to their considerably lower activation barriers vis-à-vis the gallanediyl monomers, :GaAr. This pathway was preferred over the [2 + 2] cycloaddition of olefin to monomeric…
A Cation-Captured Palladium(0) Anion: Synthesis, Structure, and Bonding of [PdBr(PPh3)2]− Ligated by an N-Heterocyclic Phosphenium Cation
Unsaturated N-heterocyclic phosphenium cations (uNHP) stabilize the [Pd0(PR3)2X]− anion proposed over the past decade to be the crucial but elusive intermediate in palladium-catalyzed cross-coupling reactions (X = halide). Insertion of metal into the P−Br bond of the precursor mesityl-substituted bromophosphine gives the structurally characterized Pd(0)-phosphenium complex (uNHPMes)Pd(PPh3)2Br, which features a long Pd−Br bond (2.7240(9) Å) and the shortest known Pd−P bond (2.1166(17) Å). The reaction is proposed to proceed by an associative pathway involving a Pd-bromophosphine complex that undergoes P-to-Pd bromide transfer. peerReviewed