Abilities of Different Electron Donors (D) to Engage in a P center dot center dot center dot D Noncovalent Interaction

作者：Scheiner Steve^*; Adhikari Upendra

来源：Journal of Physical Chemistry A, 2011, 115(40): 11101-11110.

DOI：10.1021/jp2082787

Previous work has documented. the ability of the P atom to form; a direct attractive noncovalent interaction with a N atom, based in large measure on the charge transfer from the N lone pair into the sigma* antibonding orbital of the P-H that is turned away from the N atom. The present work a considers whether other atoms, namely, O and S can also participate as electron donors, and in which bonding environments. Also considered are the pi-systems of multiply bonded C atoms. Unlike an earlier observation that the interaction is unaffected by the nature of the electron-acceptor atom, there is strong sensitivity to the donor. The P center dot center dot center dot D binding energy diminishes in the order D = NH(3) > H(2)CO > H(2)CS > H(2)S different from the patterns observed in both H and halogen bonds. The P center dot center dot center dot D interactions are comparable to, and in some cases stronger than, the analogous H-bonds formed by HOH as proton donor. The Cirbon pi stenns form surprisingly strong P center dot center dot center dot D complexes, augmented by the back-donation from the P lone pair to the C-C pi* antibond, which surpass the strengths of H-bonds, even some with HF as proton donor.

• 出版日期2011-10-13