0000000000441977
AUTHOR
Nathan Jones
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…
Synthesis, Reactivity, and Computational Analysis of Halophosphines Supported by Dianionic Guanidinate Ligands
The reported chemistry and reactivity of guanidinate supported group 15 elements in the +3 oxidation state, particularly phosphorus, is limited when compared to their ubiquity in supporting metallic elements across the periodic table. We have synthesized a series of chlorophosphines utilizing homo- and heteroleptic (dianionic)guanidinates and have completed a comprehensive study of their reactivity. Most notable is the reluctancy of these four-membered rings to form the corresponding N-heterocyclic phosphenium cations, the tendency to chemically and thermally eliminate carbodiimide, and the scarcely observed ring expansion by insertion of a chloro(imino)phosphine into a P–N bond of the P–N–…
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