0000000000441975
AUTHOR
Michael Jennings
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…
Extending the Series: Synthesis and Characterization of a Dicationic N-Heterocyclic Selenium Carbene Analogue
The room-temperature reaction between the Dipp2DAB ligand, SnCl2, and SeCl4 results in the quantitative formation of a dicationic N-heterocyclic “carbenoid”. This represents the first example of a chalcogenium dication that mimics the ubiquitous Arduengo-type carbenes; however, the electronic structure is significantly different. peerReviewed