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Title

FCl:PCX complexes: Old and new types of halogen bonds

AuthorsAlkorta, Ibon ; Sanche; Sánchez-Sanz, Goar; Elguero, José ; Del Bene, Janet E.
Issue Date2012
PublisherAmerican Chemical Society
CitationThe journal of physical chemistry, A, Molecules, spectroscopy, kinetics, environment & general theory 116: 2300- 2308 (2012)
AbstractMP2/aug′-cc-pVTZ calculations have been performed to investigate the halogen-bonded complexes FCl:PCX, for X = NC, CN, F, H, CCH, CCF, CH 3, Li, and Na. Although stable complexes with a F- Cl•••P halogen bond exist that form through the lone pair at P (configuration I), except for FCl:PCCN, the more stable complexes are those in which FCl interacts with the C≡P triple bond through a perturbed π system (configuration II). In complexes I, the nature of the halogen bond changes from traditional to chlorine-shared and the interaction energies increase, as the electron-donating ability of X increases. The anionic complex FCl:PC - has a chlorine-transferred halogen bond. SAPT analyses indicate that configuration I complexes with traditional halogen bonds are stabilized primarily by the dispersion interaction. The electrostatic interaction is the most important for configuration I complexes with chlorine-shared halogen bonds and for configuration II complexes except for FCl:PCNa for which the induction term is most important. The F-Cl stretching frequency is red-shifted upon complexation. EOM-CCSD/(qzp,qz2p) spin-spin coupling constants have been obtained for all FCl:PCX complexes with configuration I. 1J(F-Cl) decreases upon complexation. 2XJ(F-P) values are quadratically dependent upon the F-P distance and are very sensitive to halogen-bond type. 1XJ(Cl-P) tends to increase as the Cl-P distance decreases but then decreases dramatically in the chlorine-transferred complex FCl:PC - as the Cl-P interaction approaches that of a covalent Cl-P bond. Values of 1J(F-Cl) for configuration II are reduced relative to configuration I, reflecting the longer F-Cl distances in II compared to those of the neutral complexes of I. Although the F-P and Cl-P distances in configuration II complexes are shorter than these distances in the corresponding configuration I complexes, 2XJ(F-P) and 1XJ(Cl-P) values are significantly reduced, indicating that coupling through the perturbed C-P π bond is less efficient. The nature of F-P coupling for configuration II is also significantly different, as evidenced by the relative importance of PSO, FC, and SD components. © 2012 American Chemical Society.
URIhttp://hdl.handle.net/10261/62287
DOI10.1021/jp211451y
Identifiersdoi: 10.1021/jp211451y
issn: 1089-5639
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