Density functional theory calculations of Ti - TEMPO complexes: Influence of ancillary ligation on the strength of the Ti - O bond

Kuo Wei Huang; Joseph H. Han; Charles B. Musgrave; Robert M. Waymouth

doi:10.1021/om060148c

Density functional theory calculations of Ti - TEMPO complexes: Influence of ancillary ligation on the strength of the Ti - O bond

Kuo Wei Huang, Joseph H. Han, Charles B. Musgrave^*, Robert M. Waymouth

^*Corresponding author for this work

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

18 Scopus citations

Abstract

A series of mono(cyclopentadienyl)titanium TEMPO (2,2,6,6- tetramethylpiperidine-N-oxyl) complexes were investigated by density functional theory (DFT) calculations to study the influence of the ligands on the Ti - O bond energies. Mono-Cp complexes with pendant amino groups were found to possess significantly weaker Ti - O bonds than those lacking pendant donor ligands. On the basis of DFT predictions, a novel mono-Cp pendant dimethylamino complex, Cp ^NTiCl ₂(TEMPO) (12; Cp ^N = C ₅H ₄CH ₂CH ₂N(CH ₃) ₂), was identified as a mono-Cp titanium TEMPO complex with a weak Ti - O bond (25 kcal/mol). The calculated bond energy of this complex is comparable to that of Cp ₂TiCl(TEMPO) (3; 17 kcal/mol). Thermolysis of 12 in the presence of CC1 ₄ at 100 °C resulted in the formation of Cp ^NTiCl ₃, consistent with the predicted low Ti - O bond energy.

Original language	English (US)
Pages (from-to)	3317-3323
Number of pages	7
Journal	Organometallics
Volume	25
Issue number	14
DOIs	https://doi.org/10.1021/om060148c
State	Published - Jul 3 2006
Externally published	Yes

ASJC Scopus subject areas

Inorganic Chemistry
Physical and Theoretical Chemistry
Organic Chemistry

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@article{a1033a25706e43f59fec1b0b973b99b5,

title = "Density functional theory calculations of Ti - TEMPO complexes: Influence of ancillary ligation on the strength of the Ti - O bond",

abstract = "A series of mono(cyclopentadienyl)titanium TEMPO (2,2,6,6- tetramethylpiperidine-N-oxyl) complexes were investigated by density functional theory (DFT) calculations to study the influence of the ligands on the Ti - O bond energies. Mono-Cp complexes with pendant amino groups were found to possess significantly weaker Ti - O bonds than those lacking pendant donor ligands. On the basis of DFT predictions, a novel mono-Cp pendant dimethylamino complex, Cp NTiCl 2(TEMPO) (12; Cp N = C 5H 4CH 2CH 2N(CH 3) 2), was identified as a mono-Cp titanium TEMPO complex with a weak Ti - O bond (25 kcal/mol). The calculated bond energy of this complex is comparable to that of Cp 2TiCl(TEMPO) (3; 17 kcal/mol). Thermolysis of 12 in the presence of CC1 4 at 100 °C resulted in the formation of Cp NTiCl 3, consistent with the predicted low Ti - O bond energy.",

author = "Huang, {Kuo Wei} and Han, {Joseph H.} and Musgrave, {Charles B.} and Waymouth, {Robert M.}",

year = "2006",

month = jul,

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doi = "10.1021/om060148c",

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volume = "25",

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journal = "Organometallics",

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TY - JOUR

T1 - Density functional theory calculations of Ti - TEMPO complexes

T2 - Influence of ancillary ligation on the strength of the Ti - O bond

AU - Huang, Kuo Wei

AU - Han, Joseph H.

AU - Musgrave, Charles B.

AU - Waymouth, Robert M.

PY - 2006/7/3

Y1 - 2006/7/3

N2 - A series of mono(cyclopentadienyl)titanium TEMPO (2,2,6,6- tetramethylpiperidine-N-oxyl) complexes were investigated by density functional theory (DFT) calculations to study the influence of the ligands on the Ti - O bond energies. Mono-Cp complexes with pendant amino groups were found to possess significantly weaker Ti - O bonds than those lacking pendant donor ligands. On the basis of DFT predictions, a novel mono-Cp pendant dimethylamino complex, Cp NTiCl 2(TEMPO) (12; Cp N = C 5H 4CH 2CH 2N(CH 3) 2), was identified as a mono-Cp titanium TEMPO complex with a weak Ti - O bond (25 kcal/mol). The calculated bond energy of this complex is comparable to that of Cp 2TiCl(TEMPO) (3; 17 kcal/mol). Thermolysis of 12 in the presence of CC1 4 at 100 °C resulted in the formation of Cp NTiCl 3, consistent with the predicted low Ti - O bond energy.

AB - A series of mono(cyclopentadienyl)titanium TEMPO (2,2,6,6- tetramethylpiperidine-N-oxyl) complexes were investigated by density functional theory (DFT) calculations to study the influence of the ligands on the Ti - O bond energies. Mono-Cp complexes with pendant amino groups were found to possess significantly weaker Ti - O bonds than those lacking pendant donor ligands. On the basis of DFT predictions, a novel mono-Cp pendant dimethylamino complex, Cp NTiCl 2(TEMPO) (12; Cp N = C 5H 4CH 2CH 2N(CH 3) 2), was identified as a mono-Cp titanium TEMPO complex with a weak Ti - O bond (25 kcal/mol). The calculated bond energy of this complex is comparable to that of Cp 2TiCl(TEMPO) (3; 17 kcal/mol). Thermolysis of 12 in the presence of CC1 4 at 100 °C resulted in the formation of Cp NTiCl 3, consistent with the predicted low Ti - O bond energy.

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U2 - 10.1021/om060148c

DO - 10.1021/om060148c

M3 - Article

AN - SCOPUS:33746616021

SN - 0276-7333

VL - 25

SP - 3317

EP - 3323

JO - Organometallics

JF - Organometallics

IS - 14

ER -

Density functional theory calculations of Ti - TEMPO complexes: Influence of ancillary ligation on the strength of the Ti - O bond

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