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

Research output: Contribution to journalArticle

4 Citations (Scopus)

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 languageEnglish (US)
Pages (from-to)705-711
Number of pages7
JournalPolyhedron
Volume17
Issue number5-6
StatePublished - 1998

Fingerprint

Hydrocarbons
Photoelectrons
Molecular Structure
Ionization
Electronic structure
photoelectrons
Nitrogen
Gases
Metals
Nuclear magnetic resonance
X-Rays
Single crystals
electronic structure
Ligands
ionization
X rays
preparation
nuclear magnetic resonance
Temperature
single crystals

Keywords

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

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

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

In: Polyhedron, Vol. 17, No. 5-6, 1998, p. 705-711.

Research output: Contribution to journalArticle

@article{fde52b913d834d788fd08d6e0e0eb6f7,
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}",
year = "1998",
language = "English (US)",
volume = "17",
pages = "705--711",
journal = "Polyhedron",
issn = "0277-5387",
publisher = "Elsevier Limited",
number = "5-6",

}

TY - JOUR

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)

UR - http://www.scopus.com/inward/record.url?scp=0040585560&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0040585560&partnerID=8YFLogxK

M3 - Article

VL - 17

SP - 705

EP - 711

JO - Polyhedron

JF - Polyhedron

SN - 0277-5387

IS - 5-6

ER -