J. Phys. Chem. A, 119, 3125–3133 (2015)

DOI: 10.1021/acs.jpca.5b00944

P···N Pnicogen Bonds in Cationic Complexes of F4P+ and F3HP+ with Nitrogen Bases

Ab initio MP2/aug’-cc-pVTZ calculations have been carried out on cationic pnicogen-bonded complexes F4P+:N-base and F3HP+:N-base, with linear Fax–P···N and Hax-P···N, respectively. The bases include the sp3-hybridized nitrogen bases NH3, NClH2, NFH2, NCl2H, NCl3, NFCl2, NF2H, NF2Cl, and NF3, and the sp bases NCNH2, NCCH3, NP, NCOH, NCCl, NCH, NCF, NCCN, and N2. The binding energies of these complexes span a wide range, from −15 to −180 kJ mol–1, as do the P–N distances, which vary from 1.89 to 3.11 Å. There is a gap in the P–N distances between 2.25 and 2.53 Å in which no complexes are found. Thus, the equilibrium complexes may be classified as inner or outer complexes based on the value of the P–N distance. Inner complexes have P···N bonds with varying degrees of covalent character, whereas outer complexes are stabilized by intermolecular P···N bonds with little or no covalency. Charge-transfer stabilizes these pnicogen-bonded complexes. For complexes F4P+:N-base, the dominant charge-transfer interaction is from the lone pair on N to the σ*P–Faxorbital. In addition, there are three other charge-transfer interactions from the lone pair on N to the σ*P–Feq orbitals, which taken together, are more stabilizing than the interaction involving σ*P–Fax. In contrast, the dominant charge-transfer interaction for complexes F3HP+:N-base is from the lone pair on N to the σ*P–Feq orbitals. Computed EOM-CCSD Fermi-contact terms are excellent approximations to the total spin–spin coupling constants 1pJ(P–N) and 1J(P–Hax), but are poor approximations to 1J(P–Fax). 1pJ(P–N) values increase with decreasing P–N distance, approach a maximum, and then decrease and change sign as the P–N distance further decreases and the pnicogen bond acquires increased covalency. 1J(P–Fax) values for F4P+:N-base complexes increase with decreasing distance. Although the P–Hax distance changes very little in complexes F3HP+:N-base, patterns exist which suggest that changes in 1J(P–Hax) reflect the hybridization of the nitrogen base and whether the complex is an inner or outer complex.

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