Charge density analysis of the (C-C)→Ti agostic interactions in a titanacyclobutane complex

Stephan Scheins; Marc Messerschmidt; Milan Gembicky; Mateusz Pitak; Anatoliy Volkov; Philip Coppens; Benjamin G. Harvey; Gregory C. Turpin; Atta M. Arif; Richard D. Ernst

doi:10.1021/ja807649k

Charge density analysis of the (C-C)→Ti agostic interactions in a titanacyclobutane complex

Stephan Scheins, Marc Messerschmidt, Milan Gembicky, Mateusz Pitak, Anatoliy Volkov, Philip Coppens, Benjamin G. Harvey, Gregory C. Turpin, Atta M. Arif, Richard D. Ernst

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

42 Scopus citations

Abstract

The experimental electron density study of Ti(C ₅H ₄Me) ₂[(CH ₂) ₂CMe ₂] provides direct evidence for the presence of (C-C)→Ti agostic interactions. In accord with the model of Scherer and McGrady, the Cα-Cβ bond densities no longer show cylindrical symmetry in the vicinity of the Ti atom and differ markedly from those of the other C-C bonds. At the points along the Cα-Cβ- bond where the deviation is maximal the electron density is elongated toward the metal center. The distortion is supported by parallel theoretical calculations. A calculation on an Mo complex in which the agostic interaction is absent supports the Scherer and McGrady criterion for agostic interactions. Despite the formal do electron configuration for this Ti(IV) species, a significant nonzero population is observed for the d orbitals, the d orbital population is largest for the 6 _xy orbital, the lobes of which point toward the two Cα atoms. Of the three different basis sets for the Ti atom used in theoretical calculations with the B3LYP functional, only the 6-311++G** set for Ti agrees well with the experimental charge density distribution in the Ti-(Cα-Cβ) ₂ plane.

Original language	English (US)
Pages (from-to)	6154-6160
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	131
Issue number	17
DOIs	https://doi.org/10.1021/ja807649k
State	Published - May 6 2009
Externally published	Yes

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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@article{3a3a224f62d74deeaf81c5d1737d0eb1,

title = "Charge density analysis of the (C-C)→Ti agostic interactions in a titanacyclobutane complex",

abstract = "The experimental electron density study of Ti(C 5H 4Me) 2[(CH 2) 2CMe 2] provides direct evidence for the presence of (C-C)→Ti agostic interactions. In accord with the model of Scherer and McGrady, the Cα-Cβ bond densities no longer show cylindrical symmetry in the vicinity of the Ti atom and differ markedly from those of the other C-C bonds. At the points along the Cα-Cβ- bond where the deviation is maximal the electron density is elongated toward the metal center. The distortion is supported by parallel theoretical calculations. A calculation on an Mo complex in which the agostic interaction is absent supports the Scherer and McGrady criterion for agostic interactions. Despite the formal do electron configuration for this Ti(IV) species, a significant nonzero population is observed for the d orbitals, the d orbital population is largest for the 6 xy orbital, the lobes of which point toward the two Cα atoms. Of the three different basis sets for the Ti atom used in theoretical calculations with the B3LYP functional, only the 6-311++G** set for Ti agrees well with the experimental charge density distribution in the Ti-(Cα-Cβ) 2 plane.",

author = "Stephan Scheins and Marc Messerschmidt and Milan Gembicky and Mateusz Pitak and Anatoliy Volkov and Philip Coppens and Harvey, {Benjamin G.} and Turpin, {Gregory C.} and Arif, {Atta M.} and Ernst, {Richard D.}",

year = "2009",

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doi = "10.1021/ja807649k",

language = "English (US)",

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journal = "Journal of the American Chemical Society",

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T1 - Charge density analysis of the (C-C)→Ti agostic interactions in a titanacyclobutane complex

AU - Scheins, Stephan

AU - Messerschmidt, Marc

AU - Gembicky, Milan

AU - Pitak, Mateusz

AU - Volkov, Anatoliy

AU - Coppens, Philip

AU - Harvey, Benjamin G.

AU - Turpin, Gregory C.

AU - Arif, Atta M.

AU - Ernst, Richard D.

PY - 2009/5/6

Y1 - 2009/5/6

N2 - The experimental electron density study of Ti(C 5H 4Me) 2[(CH 2) 2CMe 2] provides direct evidence for the presence of (C-C)→Ti agostic interactions. In accord with the model of Scherer and McGrady, the Cα-Cβ bond densities no longer show cylindrical symmetry in the vicinity of the Ti atom and differ markedly from those of the other C-C bonds. At the points along the Cα-Cβ- bond where the deviation is maximal the electron density is elongated toward the metal center. The distortion is supported by parallel theoretical calculations. A calculation on an Mo complex in which the agostic interaction is absent supports the Scherer and McGrady criterion for agostic interactions. Despite the formal do electron configuration for this Ti(IV) species, a significant nonzero population is observed for the d orbitals, the d orbital population is largest for the 6 xy orbital, the lobes of which point toward the two Cα atoms. Of the three different basis sets for the Ti atom used in theoretical calculations with the B3LYP functional, only the 6-311++G** set for Ti agrees well with the experimental charge density distribution in the Ti-(Cα-Cβ) 2 plane.

AB - The experimental electron density study of Ti(C 5H 4Me) 2[(CH 2) 2CMe 2] provides direct evidence for the presence of (C-C)→Ti agostic interactions. In accord with the model of Scherer and McGrady, the Cα-Cβ bond densities no longer show cylindrical symmetry in the vicinity of the Ti atom and differ markedly from those of the other C-C bonds. At the points along the Cα-Cβ- bond where the deviation is maximal the electron density is elongated toward the metal center. The distortion is supported by parallel theoretical calculations. A calculation on an Mo complex in which the agostic interaction is absent supports the Scherer and McGrady criterion for agostic interactions. Despite the formal do electron configuration for this Ti(IV) species, a significant nonzero population is observed for the d orbitals, the d orbital population is largest for the 6 xy orbital, the lobes of which point toward the two Cα atoms. Of the three different basis sets for the Ti atom used in theoretical calculations with the B3LYP functional, only the 6-311++G** set for Ti agrees well with the experimental charge density distribution in the Ti-(Cα-Cβ) 2 plane.

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Charge density analysis of the (C-C)→Ti agostic interactions in a titanacyclobutane complex

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