Theoretical study on structures and aromaticities of P5 - anion, [Ti (η5-P5)]- and sandwich complex [Ti(η5-P5)2]2-

Zi Zhong Liu, Wei Quan Tian, Ji Kang Feng, Gang Zhang, Wei Qi Li

Research output: Contribution to journalArticle

32 Citations (Scopus)

Abstract

The equilibrium geometries, energies, harmonic vibrational frequencies, and nucleus independent chemical shifts (NICSs) of the ground state of P 5- (D5h) anion, the [Ti (η 5-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(η 5-P5)2]2-, and [Ti (η 5-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- (D 5h) 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 (η 5-P5)]- (C5v) and [Ti(η 5-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.

Original languageEnglish (US)
Pages (from-to)5645-5655
Number of pages11
JournalJournal of Physical Chemistry A
Volume109
Issue number25
DOIs
StatePublished - Jun 30 2005

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Chemical shift
Anions
chemical equilibrium
anions
nuclei
ring currents
Molecular orbitals
molecular orbitals
Dissection
dissection
Vibrational spectra
Binding energy
Ground state
binding energy
diagrams
fragments
harmonics
Atoms
Molecules
ground state

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

Liu, Zi Zhong ; Tian, Wei Quan ; Feng, Ji Kang ; Zhang, Gang ; Li, Wei Qi. / Theoretical study on structures and aromaticities of P5 - anion, [Ti (η5-P5)]- and sandwich complex [Ti(η5-P5)2]2-. In: Journal of Physical Chemistry A. 2005 ; Vol. 109, No. 25. pp. 5645-5655.
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title = "Theoretical study on structures and aromaticities of P5 - anion, [Ti (η5-P5)]- and sandwich complex [Ti(η5-P5)2]2-",
abstract = "The equilibrium geometries, energies, harmonic vibrational frequencies, and nucleus independent chemical shifts (NICSs) of the ground state of P 5- (D5h) anion, the [Ti (η 5-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(η 5-P5)2]2-, and [Ti (η 5-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- (D 5h) 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 (η 5-P5)]- (C5v) and [Ti(η 5-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.",
author = "Liu, {Zi Zhong} and Tian, {Wei Quan} and Feng, {Ji Kang} and Gang Zhang and Li, {Wei Qi}",
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Theoretical study on structures and aromaticities of P5 - anion, [Ti (η5-P5)]- and sandwich complex [Ti(η5-P5)2]2-. / Liu, Zi Zhong; Tian, Wei Quan; Feng, Ji Kang; Zhang, Gang; Li, Wei Qi.

In: Journal of Physical Chemistry A, Vol. 109, No. 25, 30.06.2005, p. 5645-5655.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Theoretical study on structures and aromaticities of P5 - anion, [Ti (η5-P5)]- and sandwich complex [Ti(η5-P5)2]2-

AU - Liu, Zi Zhong

AU - Tian, Wei Quan

AU - Feng, Ji Kang

AU - Zhang, Gang

AU - Li, Wei Qi

PY - 2005/6/30

Y1 - 2005/6/30

N2 - The equilibrium geometries, energies, harmonic vibrational frequencies, and nucleus independent chemical shifts (NICSs) of the ground state of P 5- (D5h) anion, the [Ti (η 5-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(η 5-P5)2]2-, and [Ti (η 5-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- (D 5h) 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 (η 5-P5)]- (C5v) and [Ti(η 5-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.

AB - The equilibrium geometries, energies, harmonic vibrational frequencies, and nucleus independent chemical shifts (NICSs) of the ground state of P 5- (D5h) anion, the [Ti (η 5-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(η 5-P5)2]2-, and [Ti (η 5-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- (D 5h) 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 (η 5-P5)]- (C5v) and [Ti(η 5-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.

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