Theoretical Study on Structures and Aromaticities of P5-Anion, [Ti (η5-P5)]-and Sandwich Complex [Ti(η5-P5)2]2-

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Abstract
The equilibrium geometries, energies, harmonic vibrational frequencies, and nucleus independent chemical shifts (NICSs) of the ground state of P5- (D5h) anion, the [Ti (η5−P5)]- fragment (C5v), and the sandwich complex [Ti(η5−P5)2]2- (D5h and D5d) are calculated by the three-parameter fit of the exchange-correlation potential suggested by Becke in conjunction with the LYP exchange potential (B3LYP) with basis sets 6-311+G(2d) (for P) and 6-311+G(2df) (for Ti). In each of the three molecules, the P−P and Ti−P bond distances are perfectly equal: five P atoms in block P5- lie in the same plane; the P−P bond distance increases and the Ti−P bond distance decreases with the order P5-, [Ti(η5−P5)2]2-, and [Ti (η5−P5)]-. The binding energy analysis, which is carried out according to the energy change of hypothetic reactions of the three species, predicts that the three species are all very stable, and [Ti (η5−P5)]- (C5v), more stable than P5- and [Ti(η5−P5)2]2- synthesized in the experiment, could be synthesized. NICS values, computed for the anion and moiety of the three species with GIAO−B3LYP, reveal that the three species all have a larger aromaticity, and NICS (0) of moiety, NICS (1) of moiety, and minimum NICS of the inner side of ring P5 plane in magnitude increase with the order P5-, [Ti(η5−P5)2]2-, and [Ti (η5−P5)]-. By analysis of the binding energetic and the molecular orbital (MO) and qualitative MO correlation diagram, and the dissection of total NICS, dissected as NICS contributions of various bonds, it is the main reason for P5- (D5h) having the larger aromaticity that the P−P σ bonds, and π bonds have the larger diatropic ring currents in which NICS contribution are negative, especially the P−P σ bond. However, in [Ti (η5−P5)]- (C5v) and [Ti(η5−P5)2]2- (D5h, and D5d), the reason is the larger and more negative diatropic ring currents in which the NICS contributions of P−P π bonds and P5−Ti bonds including π, δ, and σ bonds, especially P5−Ti bonds, are much more negative and canceled the NICS contributions of P and Ti core and lone pair electrons.