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 journalArticlepeer-review

5 Scopus citations


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
Issue number5-6
StatePublished - Jan 1 1998


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

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry


Dive into the research topics of 'Preparation, characterization and electronic structure of W<sub>2</sub>(NMe<sub>2</sub>)<sub>2</sub>(OR<sub>f</sub>)<sub>4</sub>, where R<sub>f</sub> = CMe<sub>2</sub>CF<sub>3</sub>, CMe(CF<sub>3</sub>)<sub>2</sub> and C(CF<sub>3</sub>)<sub>3</sub>, as deduced by photoelectron spectroscopic studies and the single crystal X-ray structure for Rf = OCMe(CF<sub>3</sub>)<sub>2</sub>'. Together they form a unique fingerprint.

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