A theoretical study on structures, bonding energies and aromaticity of two new series of dinuclear phosphametallocenes: (η 5 -P 5 )MM′(η 5 -P 5 ) and (η 5 - C 5 H 5 )MM′(η 5 -P 5 ) (M, M′ = Zn, Cd)

Zi Zhong Liu, Quan Tian Wei, Ji Kang Feng, Gang Zhang, Wei Qi Li, Yan Hong Cui, Chia Chung Sun

Research output: Contribution to journalArticle

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Abstract

The equilibrium geometries, the energies, the harmonic vibrational frequencies, and the nucleus independent chemical shifts (NICSs) of the ground state of (η 5 -P 5 )MM′(η 3 -P 5 ) and (η 5 -C 5 H 5 ) MM′(η 5 -P 5 ) (M, M′ = Zn, Cd) are calculated by the hybrid density functional method B3LYP with LANL2DZ basis sets. The analysis of energy and harmonic frequencies on the equilibrium geometries of both series dinuclear deca-and pentaphosphametallocenes shows that all the minima with singlet electronic state have an staggered (9° ≤ D (E-M-M-E′) ≤ 36°) conformation except for the eclipsed CpCd 2 (P 5 ) (C 5v ), and all the D 5h and the D 5d symmetric conformations are transition states while the energy differences between the most stable minimum and the transition states are very small (≤ 0.1 kcal/mol), thus, the rotation of the P 5 ring about M-M bond in all complexes is almost free. The analysis of the NBO, the Laplacian of the electron density, the electrostatic interaction energy, the bonding energy decomposition, and the molecular orbital correlation diagrams for the two series complexes reveals that the properties of all the dinuclear phosphametallocenes investigated are similar to that of the dizinc metallocenes. The M-M (or M-M′) bond in the dinuclear phosphametallocenes is a weak σ covalent bond, and the magnitude of bonding energy of the M-M (or M-M′) bond correlates with the energy difference between the energy of HOMO in M(η 5 -P 5 ) (or MCp) ( 2 A, C 5v ) fragment and the energy of HOMO-2 in [MM′(η 5 -P 5 ) 2 ] ( 1 A, D 5 , or D 5h ) [or (η 5 -P 5 )MM′Cp ( 1 A, C 5 , or C 5v )] (M, M′ = Zn, Cd). The strength of the M-M (or M-M′) bond plays a decisive role on the stability of the dinuclear phosphametallocenes. However, the M-(η 5 -P 5 ) (or M-Cp) bonding mainly is ionic. Among the different dinuclear phosphametallocenes with the same ligands, the bonding energies of the M-M (or M-M′) bond and of the M-(η 5 -P 5 ) (or M-Cp) bond decrease as M varying from Zn to Cd. Among the different phosphametallocenes with the same metals, the bonding energies of the M-M (or M-M′) bond and the M-ligand bond increase with ligand varying from the (η 5 -P 5 ) to the Cp. The negative NICSs indicate that all dinuclear phosphametallocenes have aromaticity. The various dissected bond NICS contributions reveal that the NICS contributions of the metal-ligand bond, the metal-metal bond, and the metal lone pair electrons to the overall aromaticity in the Zn-containing dinuclear phosphametallocenes are different from their counterpart contributions in the Cd-containing dinuclear phosphametallocenes, such difference causes that the overall NICSs of the Zn-containing dinuclear phosphametallocenes are more negative than that of the Cd-containing dinuclear phosphametallocenes.

Original languageEnglish (US)
Pages (from-to)2808-2818
Number of pages11
JournalEuropean Journal of Inorganic Chemistry
Issue number14
DOIs
StatePublished - Jul 17 2006

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Chemical shift
Metals
Ligands
Conformations
Covalent bonds
Geometry
Electronic states
Vibrational spectra
Organometallics
Molecular orbitals
Coulomb interactions
Ground state
Carrier concentration
Decomposition
Electrons

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

@article{d99e53b045214948ba836f1e8f02cf1b,
title = "A theoretical study on structures, bonding energies and aromaticity of two new series of dinuclear phosphametallocenes: (η 5 -P 5 )MM′(η 5 -P 5 ) and (η 5 - C 5 H 5 )MM′(η 5 -P 5 ) (M, M′ = Zn, Cd)",
abstract = "The equilibrium geometries, the energies, the harmonic vibrational frequencies, and the nucleus independent chemical shifts (NICSs) of the ground state of (η 5 -P 5 )MM′(η 3 -P 5 ) and (η 5 -C 5 H 5 ) MM′(η 5 -P 5 ) (M, M′ = Zn, Cd) are calculated by the hybrid density functional method B3LYP with LANL2DZ basis sets. The analysis of energy and harmonic frequencies on the equilibrium geometries of both series dinuclear deca-and pentaphosphametallocenes shows that all the minima with singlet electronic state have an staggered (9° ≤ D (E-M-M-E′) ≤ 36°) conformation except for the eclipsed CpCd 2 (P 5 ) (C 5v ), and all the D 5h and the D 5d symmetric conformations are transition states while the energy differences between the most stable minimum and the transition states are very small (≤ 0.1 kcal/mol), thus, the rotation of the P 5 ring about M-M bond in all complexes is almost free. The analysis of the NBO, the Laplacian of the electron density, the electrostatic interaction energy, the bonding energy decomposition, and the molecular orbital correlation diagrams for the two series complexes reveals that the properties of all the dinuclear phosphametallocenes investigated are similar to that of the dizinc metallocenes. The M-M (or M-M′) bond in the dinuclear phosphametallocenes is a weak σ covalent bond, and the magnitude of bonding energy of the M-M (or M-M′) bond correlates with the energy difference between the energy of HOMO in M(η 5 -P 5 ) (or MCp) ( 2 A, C 5v ) fragment and the energy of HOMO-2 in [MM′(η 5 -P 5 ) 2 ] ( 1 A, D 5 , or D 5h ) [or (η 5 -P 5 )MM′Cp ( 1 A, C 5 , or C 5v )] (M, M′ = Zn, Cd). The strength of the M-M (or M-M′) bond plays a decisive role on the stability of the dinuclear phosphametallocenes. However, the M-(η 5 -P 5 ) (or M-Cp) bonding mainly is ionic. Among the different dinuclear phosphametallocenes with the same ligands, the bonding energies of the M-M (or M-M′) bond and of the M-(η 5 -P 5 ) (or M-Cp) bond decrease as M varying from Zn to Cd. Among the different phosphametallocenes with the same metals, the bonding energies of the M-M (or M-M′) bond and the M-ligand bond increase with ligand varying from the (η 5 -P 5 ) to the Cp. The negative NICSs indicate that all dinuclear phosphametallocenes have aromaticity. The various dissected bond NICS contributions reveal that the NICS contributions of the metal-ligand bond, the metal-metal bond, and the metal lone pair electrons to the overall aromaticity in the Zn-containing dinuclear phosphametallocenes are different from their counterpart contributions in the Cd-containing dinuclear phosphametallocenes, such difference causes that the overall NICSs of the Zn-containing dinuclear phosphametallocenes are more negative than that of the Cd-containing dinuclear phosphametallocenes.",
author = "Liu, {Zi Zhong} and Wei, {Quan Tian} and Feng, {Ji Kang} and Gang Zhang and Li, {Wei Qi} and Cui, {Yan Hong} and Sun, {Chia Chung}",
year = "2006",
month = "7",
day = "17",
doi = "10.1002/ejic.200501148",
language = "English (US)",
pages = "2808--2818",
journal = "Chemische Berichte",
issn = "0009-2940",
publisher = "Wiley-VCH Verlag",
number = "14",

}

A theoretical study on structures, bonding energies and aromaticity of two new series of dinuclear phosphametallocenes : (η 5 -P 5 )MM′(η 5 -P 5 ) and (η 5 - C 5 H 5 )MM′(η 5 -P 5 ) (M, M′ = Zn, Cd). / Liu, Zi Zhong; Wei, Quan Tian; Feng, Ji Kang; Zhang, Gang; Li, Wei Qi; Cui, Yan Hong; Sun, Chia Chung.

In: European Journal of Inorganic Chemistry, No. 14, 17.07.2006, p. 2808-2818.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A theoretical study on structures, bonding energies and aromaticity of two new series of dinuclear phosphametallocenes

T2 - (η 5 -P 5 )MM′(η 5 -P 5 ) and (η 5 - C 5 H 5 )MM′(η 5 -P 5 ) (M, M′ = Zn, Cd)

AU - Liu, Zi Zhong

AU - Wei, Quan Tian

AU - Feng, Ji Kang

AU - Zhang, Gang

AU - Li, Wei Qi

AU - Cui, Yan Hong

AU - Sun, Chia Chung

PY - 2006/7/17

Y1 - 2006/7/17

N2 - The equilibrium geometries, the energies, the harmonic vibrational frequencies, and the nucleus independent chemical shifts (NICSs) of the ground state of (η 5 -P 5 )MM′(η 3 -P 5 ) and (η 5 -C 5 H 5 ) MM′(η 5 -P 5 ) (M, M′ = Zn, Cd) are calculated by the hybrid density functional method B3LYP with LANL2DZ basis sets. The analysis of energy and harmonic frequencies on the equilibrium geometries of both series dinuclear deca-and pentaphosphametallocenes shows that all the minima with singlet electronic state have an staggered (9° ≤ D (E-M-M-E′) ≤ 36°) conformation except for the eclipsed CpCd 2 (P 5 ) (C 5v ), and all the D 5h and the D 5d symmetric conformations are transition states while the energy differences between the most stable minimum and the transition states are very small (≤ 0.1 kcal/mol), thus, the rotation of the P 5 ring about M-M bond in all complexes is almost free. The analysis of the NBO, the Laplacian of the electron density, the electrostatic interaction energy, the bonding energy decomposition, and the molecular orbital correlation diagrams for the two series complexes reveals that the properties of all the dinuclear phosphametallocenes investigated are similar to that of the dizinc metallocenes. The M-M (or M-M′) bond in the dinuclear phosphametallocenes is a weak σ covalent bond, and the magnitude of bonding energy of the M-M (or M-M′) bond correlates with the energy difference between the energy of HOMO in M(η 5 -P 5 ) (or MCp) ( 2 A, C 5v ) fragment and the energy of HOMO-2 in [MM′(η 5 -P 5 ) 2 ] ( 1 A, D 5 , or D 5h ) [or (η 5 -P 5 )MM′Cp ( 1 A, C 5 , or C 5v )] (M, M′ = Zn, Cd). The strength of the M-M (or M-M′) bond plays a decisive role on the stability of the dinuclear phosphametallocenes. However, the M-(η 5 -P 5 ) (or M-Cp) bonding mainly is ionic. Among the different dinuclear phosphametallocenes with the same ligands, the bonding energies of the M-M (or M-M′) bond and of the M-(η 5 -P 5 ) (or M-Cp) bond decrease as M varying from Zn to Cd. Among the different phosphametallocenes with the same metals, the bonding energies of the M-M (or M-M′) bond and the M-ligand bond increase with ligand varying from the (η 5 -P 5 ) to the Cp. The negative NICSs indicate that all dinuclear phosphametallocenes have aromaticity. The various dissected bond NICS contributions reveal that the NICS contributions of the metal-ligand bond, the metal-metal bond, and the metal lone pair electrons to the overall aromaticity in the Zn-containing dinuclear phosphametallocenes are different from their counterpart contributions in the Cd-containing dinuclear phosphametallocenes, such difference causes that the overall NICSs of the Zn-containing dinuclear phosphametallocenes are more negative than that of the Cd-containing dinuclear phosphametallocenes.

AB - The equilibrium geometries, the energies, the harmonic vibrational frequencies, and the nucleus independent chemical shifts (NICSs) of the ground state of (η 5 -P 5 )MM′(η 3 -P 5 ) and (η 5 -C 5 H 5 ) MM′(η 5 -P 5 ) (M, M′ = Zn, Cd) are calculated by the hybrid density functional method B3LYP with LANL2DZ basis sets. The analysis of energy and harmonic frequencies on the equilibrium geometries of both series dinuclear deca-and pentaphosphametallocenes shows that all the minima with singlet electronic state have an staggered (9° ≤ D (E-M-M-E′) ≤ 36°) conformation except for the eclipsed CpCd 2 (P 5 ) (C 5v ), and all the D 5h and the D 5d symmetric conformations are transition states while the energy differences between the most stable minimum and the transition states are very small (≤ 0.1 kcal/mol), thus, the rotation of the P 5 ring about M-M bond in all complexes is almost free. The analysis of the NBO, the Laplacian of the electron density, the electrostatic interaction energy, the bonding energy decomposition, and the molecular orbital correlation diagrams for the two series complexes reveals that the properties of all the dinuclear phosphametallocenes investigated are similar to that of the dizinc metallocenes. The M-M (or M-M′) bond in the dinuclear phosphametallocenes is a weak σ covalent bond, and the magnitude of bonding energy of the M-M (or M-M′) bond correlates with the energy difference between the energy of HOMO in M(η 5 -P 5 ) (or MCp) ( 2 A, C 5v ) fragment and the energy of HOMO-2 in [MM′(η 5 -P 5 ) 2 ] ( 1 A, D 5 , or D 5h ) [or (η 5 -P 5 )MM′Cp ( 1 A, C 5 , or C 5v )] (M, M′ = Zn, Cd). The strength of the M-M (or M-M′) bond plays a decisive role on the stability of the dinuclear phosphametallocenes. However, the M-(η 5 -P 5 ) (or M-Cp) bonding mainly is ionic. Among the different dinuclear phosphametallocenes with the same ligands, the bonding energies of the M-M (or M-M′) bond and of the M-(η 5 -P 5 ) (or M-Cp) bond decrease as M varying from Zn to Cd. Among the different phosphametallocenes with the same metals, the bonding energies of the M-M (or M-M′) bond and the M-ligand bond increase with ligand varying from the (η 5 -P 5 ) to the Cp. The negative NICSs indicate that all dinuclear phosphametallocenes have aromaticity. The various dissected bond NICS contributions reveal that the NICS contributions of the metal-ligand bond, the metal-metal bond, and the metal lone pair electrons to the overall aromaticity in the Zn-containing dinuclear phosphametallocenes are different from their counterpart contributions in the Cd-containing dinuclear phosphametallocenes, such difference causes that the overall NICSs of the Zn-containing dinuclear phosphametallocenes are more negative than that of the Cd-containing dinuclear phosphametallocenes.

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