Speciation of [Cp*2M2O5] in polar and donor solvents

Creative Commons License

AKTAŞ P., Del Rosal I., Manoury E., DEMİRHAN F., Lledõs A., Poli R.

Chemistry - A European Journal, cilt.19, sa.12, ss.3969-3985, 2013 (SCI-Expanded) identifier identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 19 Sayı: 12
  • Basım Tarihi: 2013
  • Doi Numarası: 10.1002/chem.201203075
  • Dergi Adı: Chemistry - A European Journal
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.3969-3985
  • Anahtar Kelimeler: density functional calculations, molybdenum, solvent effects, speciation, tungsten
  • Manisa Celal Bayar Üniversitesi Adresli: Evet

Özet

The speciation of compounds [Cp*2M2O 5] (M=Mo, W; Cp*=pentamethylcyclopentadienyl) in different protic and aprotic polar solvents (methanol, dimethyl sulfoxide, acetone, acetonitrile), in the presence of variable amounts of water or acid/base, has been investigated by 1H NMR spectrometry and electrical conductivity. Specific hypotheses suggested by the experimental results have been further probed by DFT calculations. The solvent (S)-assisted ionic dissociation to generate [Cp*MO2(S)]+ and [Cp*MO 3]- takes place extensively for both metals only in water/methanol mixtures. Equilibrium amounts of the neutral hydroxido species [Cp*MO2(OH)] are generated in the presence of water, with the relative amount increasing in the order MeCN≈acetone