Speciation of [Cp*2M2O5] in Polar and Donor Solvents

Pelin Sözen-Aktaş (1, 2) , Iker Del rosal (3, 4) , Eric Manoury (1) , Funda Demirhan (2) , Agustí Lledós (4) , Rinaldo Poli (1, 5)

1 LCC - Laboratoire de chimie de coordination
2 Department of Chemistry, Faculty of Sciences & Liberal Arts, Celal Bayar University
3 LPCNO - Laboratoire de physique et chimie des nano-objets
4 UAB - Universitat Autònoma de Barcelona = Autonomous University of Barcelona = Universidad Autónoma de Barcelona
5 IUF - Institut universitaire de France

The speciation of compounds [Cp*2M2O5] (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*MO3]− 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

Mots clés: Density functional calculations; Molybdenum; Solvent effects; Speciation; Tungsten; DFT calculations; Pentamethylcyclopentadienyl

Domaines: Chimie de coordination; Chimie théorique et/ou physique

Pelin Sözen-Aktaş, Iker Del rosal, Eric Manoury, Funda Demirhan, Agustí Lledós, et al.. Speciation of [Cp*2M2O5] in Polar and Donor Solvents. Chemistry - A European Journal, 2013, 19 (12), pp.3969-3985. ⟨10.1002/chem.201203075⟩. ⟨hal-02908715⟩