Structures and bonding of the sandwich complexes [Ti(η5-E5)2]2- (E = CH, N, P, As, Sb): A theoretical study

Matthias Lein; Jan Frunzke; Gernot Frenking

doi:10.1021/ic020592h

Structures and bonding of the sandwich complexes [Ti(η⁵-E₅)₂]^2- (E = CH, N, P, As, Sb): A theoretical study

Matthias Lein, Jan Frunzke, Gernot Frenking

University of Marburg

Research output: Contribution to journal › Article › peer-review

99 Scopus citations

Abstract

Quantum chemical calculations using gradient-corrected DFT at the BP86/TZ2P level of the compounds [Ti(η⁵- E₅)₂]^2- (E = CH, N, P, As, Sb) are reported. The nature of the metal-ligand bonding has been analyzed with an energy decomposition method, and the results are compared with [Fe(η⁵-E₅)₂]. The bonding in both series of complexes is more covalent than electrostatic. The energy decomposition analysis shows that the dominant orbital interactions in the negatively charged titanium species come from the (e2′) Ti → [(η⁵-E₅)₂]^2- back-donation (δ bonding) while the covalent bonding in the iron complexes come mainly from (e₁″) (Cp^-)₂ → Fe²⁺ donation (π bonding). The nature of the metal-ligand interactions does not change very much for different ligands cyc-E₅ within the two series of compounds. The calculated bond dissociation energies for breaking one metal-ligand bond of the molecules [Ti(η⁵-E₅)₂]^2- shows for E the order P > As > Sb ≫ N ≫ CH. The central message of this work is that the complexes [Ti(η⁵-E₅)₂]^2- are δ bonded molecules.

Original language	English
Pages (from-to)	2504-2511
Number of pages	8
Journal	Inorganic Chemistry
Volume	42
Issue number	8
DOIs	https://doi.org/10.1021/ic020592h
State	Published - 21 Apr 2003
Externally published	Yes

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title = "Structures and bonding of the sandwich complexes [Ti(η5-E5)2]2- (E = CH, N, P, As, Sb): A theoretical study",

abstract = "Quantum chemical calculations using gradient-corrected DFT at the BP86/TZ2P level of the compounds [Ti(η5- E5)2]2- (E = CH, N, P, As, Sb) are reported. The nature of the metal-ligand bonding has been analyzed with an energy decomposition method, and the results are compared with [Fe(η5-E5)2]. The bonding in both series of complexes is more covalent than electrostatic. The energy decomposition analysis shows that the dominant orbital interactions in the negatively charged titanium species come from the (e2′) Ti → [(η5-E5)2]2- back-donation (δ bonding) while the covalent bonding in the iron complexes come mainly from (e1″) (Cp-)2 → Fe2+ donation (π bonding). The nature of the metal-ligand interactions does not change very much for different ligands cyc-E5 within the two series of compounds. The calculated bond dissociation energies for breaking one metal-ligand bond of the molecules [Ti(η5-E5)2]2- shows for E the order P > As > Sb ≫ N ≫ CH. The central message of this work is that the complexes [Ti(η5-E5)2]2- are δ bonded molecules.",

author = "Matthias Lein and Jan Frunzke and Gernot Frenking",

year = "2003",

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doi = "10.1021/ic020592h",

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volume = "42",

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T1 - Structures and bonding of the sandwich complexes [Ti(η5-E5)2]2- (E = CH, N, P, As, Sb)

T2 - A theoretical study

AU - Lein, Matthias

AU - Frunzke, Jan

AU - Frenking, Gernot

PY - 2003/4/21

Y1 - 2003/4/21

N2 - Quantum chemical calculations using gradient-corrected DFT at the BP86/TZ2P level of the compounds [Ti(η5- E5)2]2- (E = CH, N, P, As, Sb) are reported. The nature of the metal-ligand bonding has been analyzed with an energy decomposition method, and the results are compared with [Fe(η5-E5)2]. The bonding in both series of complexes is more covalent than electrostatic. The energy decomposition analysis shows that the dominant orbital interactions in the negatively charged titanium species come from the (e2′) Ti → [(η5-E5)2]2- back-donation (δ bonding) while the covalent bonding in the iron complexes come mainly from (e1″) (Cp-)2 → Fe2+ donation (π bonding). The nature of the metal-ligand interactions does not change very much for different ligands cyc-E5 within the two series of compounds. The calculated bond dissociation energies for breaking one metal-ligand bond of the molecules [Ti(η5-E5)2]2- shows for E the order P > As > Sb ≫ N ≫ CH. The central message of this work is that the complexes [Ti(η5-E5)2]2- are δ bonded molecules.

AB - Quantum chemical calculations using gradient-corrected DFT at the BP86/TZ2P level of the compounds [Ti(η5- E5)2]2- (E = CH, N, P, As, Sb) are reported. The nature of the metal-ligand bonding has been analyzed with an energy decomposition method, and the results are compared with [Fe(η5-E5)2]. The bonding in both series of complexes is more covalent than electrostatic. The energy decomposition analysis shows that the dominant orbital interactions in the negatively charged titanium species come from the (e2′) Ti → [(η5-E5)2]2- back-donation (δ bonding) while the covalent bonding in the iron complexes come mainly from (e1″) (Cp-)2 → Fe2+ donation (π bonding). The nature of the metal-ligand interactions does not change very much for different ligands cyc-E5 within the two series of compounds. The calculated bond dissociation energies for breaking one metal-ligand bond of the molecules [Ti(η5-E5)2]2- shows for E the order P > As > Sb ≫ N ≫ CH. The central message of this work is that the complexes [Ti(η5-E5)2]2- are δ bonded molecules.

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Structures and bonding of the sandwich complexes [Ti(η⁵-E₅)₂]^2- (E = CH, N, P, As, Sb): A theoretical study

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