The crystal structure of tetrakis(dimethylamino)titanium(IV)

M E  Davie; T  Foerster; S  Parsons; C  Pulham; D W H  Rankin; B A  Smart

doi:10.1016/j.poly.2005.10.019

The crystal structure of tetrakis(dimethylamino)titanium(IV)

M E Davie, T Foerster, S Parsons, C Pulham, D W H Rankin, B A Smart

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

Abstract

Ti(NMe2)(4) is a monomeric species in the gas phase and in solution, and this remains true on crystallisation. The crystal structure is triclinic, with space group P1, and unit cell dimensions a = 8.277(6), b = 8.407(6), c = 11.167(7) angstrom, a = 105.36(4)degrees, beta = 97.03(3)degrees and gamma = 116.01(2)degrees at 105 K. Electron -diffraction measurements show that in the gas-phase Ti(NMe2)(4) takes the form of a slightly flattened tetrahedron with overall S-4 symmetry. In the solid state the symmetry changes to C-1; the reduction of point-symmetry results from the twisting of one of the amino groups away from its gas-phase configuration. DFT calculations indicate that the energy of the C, structure lies only 0.2 kJ mol(-1) above that of the S-4 conformer. The change in structure on crystallisation can be ascribed to the avoidance of prohibitively short intermolecular methyl-methyl interactions which would have been formed had the S-4 structure been retained. (c) 2005 Elsevier Ltd. All rights reserved.

Original language	English
Pages (from-to)	923-929
Number of pages	7
Journal	Polyhedron
Volume	25
Issue number	4
DOIs	https://doi.org/10.1016/j.poly.2005.10.019
Publication status	Published - 6 Mar 2006

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@article{680905f1864a42f0927567695cb4b226,

title = "The crystal structure of tetrakis(dimethylamino)titanium(IV)",

abstract = "Ti(NMe2)(4) is a monomeric species in the gas phase and in solution, and this remains true on crystallisation. The crystal structure is triclinic, with space group P1, and unit cell dimensions a = 8.277(6), b = 8.407(6), c = 11.167(7) angstrom, a = 105.36(4)degrees, beta = 97.03(3)degrees and gamma = 116.01(2)degrees at 105 K. Electron -diffraction measurements show that in the gas-phase Ti(NMe2)(4) takes the form of a slightly flattened tetrahedron with overall S-4 symmetry. In the solid state the symmetry changes to C-1; the reduction of point-symmetry results from the twisting of one of the amino groups away from its gas-phase configuration. DFT calculations indicate that the energy of the C, structure lies only 0.2 kJ mol(-1) above that of the S-4 conformer. The change in structure on crystallisation can be ascribed to the avoidance of prohibitively short intermolecular methyl-methyl interactions which would have been formed had the S-4 structure been retained. (c) 2005 Elsevier Ltd. All rights reserved.",

author = "Davie, {M E} and T Foerster and S Parsons and C Pulham and Rankin, {D W H} and Smart, {B A}",

year = "2006",

month = mar,

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doi = "10.1016/j.poly.2005.10.019",

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T1 - The crystal structure of tetrakis(dimethylamino)titanium(IV)

AU - Davie, M E

AU - Foerster, T

AU - Parsons, S

AU - Pulham, C

AU - Rankin, D W H

AU - Smart, B A

PY - 2006/3/6

Y1 - 2006/3/6

N2 - Ti(NMe2)(4) is a monomeric species in the gas phase and in solution, and this remains true on crystallisation. The crystal structure is triclinic, with space group P1, and unit cell dimensions a = 8.277(6), b = 8.407(6), c = 11.167(7) angstrom, a = 105.36(4)degrees, beta = 97.03(3)degrees and gamma = 116.01(2)degrees at 105 K. Electron -diffraction measurements show that in the gas-phase Ti(NMe2)(4) takes the form of a slightly flattened tetrahedron with overall S-4 symmetry. In the solid state the symmetry changes to C-1; the reduction of point-symmetry results from the twisting of one of the amino groups away from its gas-phase configuration. DFT calculations indicate that the energy of the C, structure lies only 0.2 kJ mol(-1) above that of the S-4 conformer. The change in structure on crystallisation can be ascribed to the avoidance of prohibitively short intermolecular methyl-methyl interactions which would have been formed had the S-4 structure been retained. (c) 2005 Elsevier Ltd. All rights reserved.

AB - Ti(NMe2)(4) is a monomeric species in the gas phase and in solution, and this remains true on crystallisation. The crystal structure is triclinic, with space group P1, and unit cell dimensions a = 8.277(6), b = 8.407(6), c = 11.167(7) angstrom, a = 105.36(4)degrees, beta = 97.03(3)degrees and gamma = 116.01(2)degrees at 105 K. Electron -diffraction measurements show that in the gas-phase Ti(NMe2)(4) takes the form of a slightly flattened tetrahedron with overall S-4 symmetry. In the solid state the symmetry changes to C-1; the reduction of point-symmetry results from the twisting of one of the amino groups away from its gas-phase configuration. DFT calculations indicate that the energy of the C, structure lies only 0.2 kJ mol(-1) above that of the S-4 conformer. The change in structure on crystallisation can be ascribed to the avoidance of prohibitively short intermolecular methyl-methyl interactions which would have been formed had the S-4 structure been retained. (c) 2005 Elsevier Ltd. All rights reserved.

U2 - 10.1016/j.poly.2005.10.019

DO - 10.1016/j.poly.2005.10.019

M3 - Article

SN - 0277-5387

VL - 25

SP - 923

EP - 929

JO - Polyhedron

JF - Polyhedron

IS - 4

ER -

The crystal structure of tetrakis(dimethylamino)titanium(IV)

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