Stretching the P–C Bond. Variations on Carbenes and Phosphanes

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2020-04, Vol.124 (13), p.2660-2671
• Main Authors: Buzsáki, Dániel, Kelemen, Zsolt, Nyulászi, László
• Format: Article
• Language: English
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.0c00641

The stability and the structure of adducts formed between four substituted phosphanes (PX3, X:H, F, Cl, and NMe2) and 11 different carbenes have been investigated by DFT calculations. In most cases, the structure of the adducts depends strongly on the stability of the carbene itself, exhibiting a linear correlation with the increasing dissociation energy of the adduct. Carbenes of low stability form phosphorus ylides (F), which can be described as phosphane → carbene adducts supported with some back-bonding. The most stable carbenes, which have high energy lone pair, do not form stable F-type structures but carbene → phosphane adducts (E-type structure), utilizing the low-lying lowest unoccupied molecular orbital (LUMO) of the phosphane (with electronegative substituents), benefiting also from the carbene–pnictogen interaction. Especially noteworthy is the case of PCl3, which has an extremely low energy LUMO in its T-shaped form. Although this PCl3 structure is a transition state of rather high energy, the large stabilization energy of the complex makes this carbene–phosphane adduct stable. Most interestingly, in case of carbenes with medium stability both F- and E-type structures could be optimized, giving rise to bond-stretch isomerism. Likewise, for phosphorus ylides (F), the stability of the adducts G formed from carbenes with hypovalent phosphorus (PXphosphinidene) is in a linear relationship with the stabilization of the carbene. Adducts of carbenes with hypervalent phosphorus (PX5) are the most stable when X is electronegative, and the carbene is highly nucleophilic.