On the suppression mechanism of the Pseudo-Jahn-Teller effect in middle E 6 (E = P, As, Sb) rings of triple-decker sandwich complexes

Alexander S. Ivanov; Konstantin V. Bozhenko; Alexander I. Boldyrev

doi:10.1021/ic300786w

On the suppression mechanism of the Pseudo-Jahn-Teller effect in middle E ₆ (E = P, As, Sb) rings of triple-decker sandwich complexes

Alexander S. Ivanov
, Konstantin V. Bozhenko
, Alexander I. Boldyrev

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

42 Scopus citations

Abstract

Quantum chemical calculations of the CpMoE ₆MoCp (E = P, As, Sb) triple-decker sandwich complexes showed that E ₆ fragments in the central decks of the complexes are planar. Analysis of molecular orbitals involved in vibrational coupling demonstrated that filling the unoccupied molecular orbitals involved in vibronic coupling with electron pairs of Mo atoms suppresses the PJT effect in the CpMoE ₆MoCp (E = P, As, Sb) sandwich, with the E ₆ ring becoming planar (D _6h) upon complex formation. The AdNDP analysis revealed that bonding between C ₅H ₅ ^- units and Mo atoms has a significant ionic contribution, while bonding between Mo atoms and E ₆ fragment becomes appreciably covalent through the δ-type M → L back-donation mechanism.

Original language	English
Pages (from-to)	8868-8872
Number of pages	5
Journal	Inorganic Chemistry
Volume	51
Issue number	16
DOIs	https://doi.org/10.1021/ic300786w
State	Published - Aug 20 2012
Externally published	Yes

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title = "On the suppression mechanism of the Pseudo-Jahn-Teller effect in middle E 6 (E = P, As, Sb) rings of triple-decker sandwich complexes",

abstract = "Quantum chemical calculations of the CpMoE 6MoCp (E = P, As, Sb) triple-decker sandwich complexes showed that E 6 fragments in the central decks of the complexes are planar. Analysis of molecular orbitals involved in vibrational coupling demonstrated that filling the unoccupied molecular orbitals involved in vibronic coupling with electron pairs of Mo atoms suppresses the PJT effect in the CpMoE 6MoCp (E = P, As, Sb) sandwich, with the E 6 ring becoming planar (D 6h) upon complex formation. The AdNDP analysis revealed that bonding between C 5H 5 - units and Mo atoms has a significant ionic contribution, while bonding between Mo atoms and E 6 fragment becomes appreciably covalent through the δ-type M → L back-donation mechanism.",

author = "Ivanov, \{Alexander S.\} and Bozhenko, \{Konstantin V.\} and Boldyrev, \{Alexander I.\}",

year = "2012",

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doi = "10.1021/ic300786w",

language = "English",

volume = "51",

pages = "8868--8872",

journal = "Inorganic Chemistry",

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TY - JOUR

T1 - On the suppression mechanism of the Pseudo-Jahn-Teller effect in middle E 6 (E = P, As, Sb) rings of triple-decker sandwich complexes

AU - Ivanov, Alexander S.

AU - Bozhenko, Konstantin V.

AU - Boldyrev, Alexander I.

PY - 2012/8/20

Y1 - 2012/8/20

N2 - Quantum chemical calculations of the CpMoE 6MoCp (E = P, As, Sb) triple-decker sandwich complexes showed that E 6 fragments in the central decks of the complexes are planar. Analysis of molecular orbitals involved in vibrational coupling demonstrated that filling the unoccupied molecular orbitals involved in vibronic coupling with electron pairs of Mo atoms suppresses the PJT effect in the CpMoE 6MoCp (E = P, As, Sb) sandwich, with the E 6 ring becoming planar (D 6h) upon complex formation. The AdNDP analysis revealed that bonding between C 5H 5 - units and Mo atoms has a significant ionic contribution, while bonding between Mo atoms and E 6 fragment becomes appreciably covalent through the δ-type M → L back-donation mechanism.

AB - Quantum chemical calculations of the CpMoE 6MoCp (E = P, As, Sb) triple-decker sandwich complexes showed that E 6 fragments in the central decks of the complexes are planar. Analysis of molecular orbitals involved in vibrational coupling demonstrated that filling the unoccupied molecular orbitals involved in vibronic coupling with electron pairs of Mo atoms suppresses the PJT effect in the CpMoE 6MoCp (E = P, As, Sb) sandwich, with the E 6 ring becoming planar (D 6h) upon complex formation. The AdNDP analysis revealed that bonding between C 5H 5 - units and Mo atoms has a significant ionic contribution, while bonding between Mo atoms and E 6 fragment becomes appreciably covalent through the δ-type M → L back-donation mechanism.

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U2 - 10.1021/ic300786w

DO - 10.1021/ic300786w

M3 - Article

AN - SCOPUS:84865275187

SN - 0020-1669

VL - 51

SP - 8868

EP - 8872

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 16

ER -

On the suppression mechanism of the Pseudo-Jahn-Teller effect in middle E ₆ (E = P, As, Sb) rings of triple-decker sandwich complexes

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