Preparation, characterization and electronic structure of W2(NMe2)2(ORf)4, where Rf = CMe2CF3, CMe(CF3)2 and C(CF3)3, as deduced by photoelectron spectroscopic studies and the single crystal X-ray structure for Rf = OCMe(CF3)2

Theodore A. Budzichowski; Malcolm H. Chisholm; Darin B. Tiedtke; Nadine E. Gruhn; Dennis L. Lichtenberger

doi:10.1016/S0277-5387(97)00360-4

Preparation, characterization and electronic structure of W₂(NMe₂)₂(OR_f)₄, where R_f = CMe₂CF₃, CMe(CF₃)₂ and C(CF₃)₃, as deduced by photoelectron spectroscopic studies and the single crystal X-ray structure for Rf = OCMe(CF₃)₂

Theodore A. Budzichowski
, Malcolm H. Chisholm
, Darin B. Tiedtke
, Nadine E. Gruhn
, Dennis L. Lichtenberger

Chemistry & Biochemistry - Sci

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

5 Scopus citations

Abstract

The compounds W₂(NMe₂)₂(OCMe₂CF₃) ₄, 1, W₂(NMe₂)₂(OCMe(CF₃) ₂)₄, 2, and W₂(NMe₂)₂ (OC(CF₃)₃)₄, 3, have been obtained from reactions between W₂(NMe₂)₆ and the respective fluoroalcohol in hydrocarbon solvents. The compounds 2 and 3 appear inert to further reaction with their fluoroalcohol at room temperature while 1 reacts further to give W₂(OCMe₂CF₃)₆. In solution NMR data indicate that all three compounds exist in a mixture of anti-and gauche-rotamers with restricted rotations about both W - N and W≡W bonds on the NMR time-scale. The solid-state molecular structure of 2 reveals a centrosymmetric NO₂W≡WO₂N core with W - W = 2.3107(6) Å, W - N = 1.914(4) Å, W - O = 1.959(3) and 1.907(3) Å and angles W - W - O/N within the range 100 to 110°. The gas phase photoelectron spectra for 1, 2 and 3 were obtained and are compared with that for W₂(NMe₂)₆. The introduction of the fluoroalkoxide ligands has a pronounced effect in stabilizing the metal and nitrogen lone-pair based ionizations, and this effect is amplified by the successive replacement of each methyl group by a trifluoromethyl group. Also for the compounds 1, 2, and 3 the lowest ionization bands clearly reveal the removal of the degeneracy of the W - W π MOs as expected for anti and gauche complexes.

Original language	English (US)
Pages (from-to)	705-711
Number of pages	7
Journal	Polyhedron
Volume	17
Issue number	5-6
DOIs	https://doi.org/10.1016/S0277-5387(97)00360-4
State	Published - 1998

Keywords

Photoelectron spectroscopic studies
Single crystal X-ray structure
W(NMe)(OR)

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/S0277-5387(97)00360-4

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Budzichowski, T. A., Chisholm, M. H., Tiedtke, D. B., Gruhn, N. E., & Lichtenberger, D. L. (1998). Preparation, characterization and electronic structure of W₂(NMe₂)₂(OR_f)₄, where R_f = CMe₂CF₃, CMe(CF₃)₂ and C(CF₃)₃, as deduced by photoelectron spectroscopic studies and the single crystal X-ray structure for Rf = OCMe(CF₃)₂. Polyhedron, 17(5-6), 705-711. https://doi.org/10.1016/S0277-5387(97)00360-4

Preparation, characterization and electronic structure of W₂(NMe₂)₂(OR_f)₄, where R_f = CMe₂CF₃, CMe(CF₃)₂ and C(CF₃)₃, as deduced by photoelectron spectroscopic studies and the single crystal X-ray structure for Rf = OCMe(CF₃)₂. / Budzichowski, Theodore A.; Chisholm, Malcolm H.; Tiedtke, Darin B. et al.
In: Polyhedron, Vol. 17, No. 5-6, 1998, p. 705-711.

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

Budzichowski, TA, Chisholm, MH, Tiedtke, DB, Gruhn, NE & Lichtenberger, DL 1998, 'Preparation, characterization and electronic structure of W₂(NMe₂)₂(OR_f)₄, where R_f = CMe₂CF₃, CMe(CF₃)₂ and C(CF₃)₃, as deduced by photoelectron spectroscopic studies and the single crystal X-ray structure for Rf = OCMe(CF₃)₂', Polyhedron, vol. 17, no. 5-6, pp. 705-711. https://doi.org/10.1016/S0277-5387(97)00360-4

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title = "Preparation, characterization and electronic structure of W2(NMe2)2(ORf)4, where Rf = CMe2CF3, CMe(CF3)2 and C(CF3)3, as deduced by photoelectron spectroscopic studies and the single crystal X-ray structure for Rf = OCMe(CF3)2",

abstract = "The compounds W2(NMe2)2(OCMe2CF3) 4, 1, W2(NMe2)2(OCMe(CF3) 2)4, 2, and W2(NMe2)2 (OC(CF3)3)4, 3, have been obtained from reactions between W2(NMe2)6 and the respective fluoroalcohol in hydrocarbon solvents. The compounds 2 and 3 appear inert to further reaction with their fluoroalcohol at room temperature while 1 reacts further to give W2(OCMe2CF3)6. In solution NMR data indicate that all three compounds exist in a mixture of anti-and gauche-rotamers with restricted rotations about both W - N and W≡W bonds on the NMR time-scale. The solid-state molecular structure of 2 reveals a centrosymmetric NO2W≡WO2N core with W - W = 2.3107(6) {\AA}, W - N = 1.914(4) {\AA}, W - O = 1.959(3) and 1.907(3) {\AA} and angles W - W - O/N within the range 100 to 110°. The gas phase photoelectron spectra for 1, 2 and 3 were obtained and are compared with that for W2(NMe2)6. The introduction of the fluoroalkoxide ligands has a pronounced effect in stabilizing the metal and nitrogen lone-pair based ionizations, and this effect is amplified by the successive replacement of each methyl group by a trifluoromethyl group. Also for the compounds 1, 2, and 3 the lowest ionization bands clearly reveal the removal of the degeneracy of the W - W π MOs as expected for anti and gauche complexes.",

keywords = "Photoelectron spectroscopic studies, Single crystal X-ray structure, W(NMe)(OR)",

author = "Budzichowski, \{Theodore A.\} and Chisholm, \{Malcolm H.\} and Tiedtke, \{Darin B.\} and Gruhn, \{Nadine E.\} and Lichtenberger, \{Dennis L.\}",

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doi = "10.1016/S0277-5387(97)00360-4",

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T1 - Preparation, characterization and electronic structure of W2(NMe2)2(ORf)4, where Rf = CMe2CF3, CMe(CF3)2 and C(CF3)3, as deduced by photoelectron spectroscopic studies and the single crystal X-ray structure for Rf = OCMe(CF3)2

AU - Budzichowski, Theodore A.

AU - Chisholm, Malcolm H.

AU - Tiedtke, Darin B.

AU - Gruhn, Nadine E.

AU - Lichtenberger, Dennis L.

PY - 1998

Y1 - 1998

N2 - The compounds W2(NMe2)2(OCMe2CF3) 4, 1, W2(NMe2)2(OCMe(CF3) 2)4, 2, and W2(NMe2)2 (OC(CF3)3)4, 3, have been obtained from reactions between W2(NMe2)6 and the respective fluoroalcohol in hydrocarbon solvents. The compounds 2 and 3 appear inert to further reaction with their fluoroalcohol at room temperature while 1 reacts further to give W2(OCMe2CF3)6. In solution NMR data indicate that all three compounds exist in a mixture of anti-and gauche-rotamers with restricted rotations about both W - N and W≡W bonds on the NMR time-scale. The solid-state molecular structure of 2 reveals a centrosymmetric NO2W≡WO2N core with W - W = 2.3107(6) Å, W - N = 1.914(4) Å, W - O = 1.959(3) and 1.907(3) Å and angles W - W - O/N within the range 100 to 110°. The gas phase photoelectron spectra for 1, 2 and 3 were obtained and are compared with that for W2(NMe2)6. The introduction of the fluoroalkoxide ligands has a pronounced effect in stabilizing the metal and nitrogen lone-pair based ionizations, and this effect is amplified by the successive replacement of each methyl group by a trifluoromethyl group. Also for the compounds 1, 2, and 3 the lowest ionization bands clearly reveal the removal of the degeneracy of the W - W π MOs as expected for anti and gauche complexes.

AB - The compounds W2(NMe2)2(OCMe2CF3) 4, 1, W2(NMe2)2(OCMe(CF3) 2)4, 2, and W2(NMe2)2 (OC(CF3)3)4, 3, have been obtained from reactions between W2(NMe2)6 and the respective fluoroalcohol in hydrocarbon solvents. The compounds 2 and 3 appear inert to further reaction with their fluoroalcohol at room temperature while 1 reacts further to give W2(OCMe2CF3)6. In solution NMR data indicate that all three compounds exist in a mixture of anti-and gauche-rotamers with restricted rotations about both W - N and W≡W bonds on the NMR time-scale. The solid-state molecular structure of 2 reveals a centrosymmetric NO2W≡WO2N core with W - W = 2.3107(6) Å, W - N = 1.914(4) Å, W - O = 1.959(3) and 1.907(3) Å and angles W - W - O/N within the range 100 to 110°. The gas phase photoelectron spectra for 1, 2 and 3 were obtained and are compared with that for W2(NMe2)6. The introduction of the fluoroalkoxide ligands has a pronounced effect in stabilizing the metal and nitrogen lone-pair based ionizations, and this effect is amplified by the successive replacement of each methyl group by a trifluoromethyl group. Also for the compounds 1, 2, and 3 the lowest ionization bands clearly reveal the removal of the degeneracy of the W - W π MOs as expected for anti and gauche complexes.

KW - Photoelectron spectroscopic studies

KW - Single crystal X-ray structure

KW - W(NMe)(OR)

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