Aqueous Reduction of [Cp*2W2O5]: Characterization of the Triangular Clusters [Cp*3W3O4(OH)2]2+ and [Cp*3W3O6]+ – Comparison with Molybdenum

Chiara Dinoi (1) , Pelin Sözen (2) , Gülnur Taban (2) , Deniz Demir (2) , Funda Demirhan (2) , Petr Prikhodchenko (3) , Jenny Gun (3) , Ovadia Lev (3) , Jean-Claude Daran (1) , Rinaldo Poli (1)

1 LCC - Laboratoire de chimie de coordination
2 Department of Chemistry, Faculty of Sciences & Liberal Arts, Celal Bayar University
3 Institute of Chemistry, The Hebrew University of Jerusalem

Zinc reduction of Cp*2W2O5 in an acidified water–methanol medium affords the green 3‐electron trinuclear cluster [Cp*3W3O4(OH)2]2+, isolated and crystallographically characterized as the triflate salt, 1. Upon exposure to air, this complex is oxidized to a related 2‐electron cluster, [Cp*3W3O6]+, which was crystallized and characterized in three different salts, 2–4. The 3‐electron cluster exhibits a near‐tetragonal frozen‐glass EPR spectrum, and it shows evidence of coupling of the unpaired electron to only one of the three W atoms. The two‐electron cluster is diamagnetic. An electrospray ionization MSn study revealed a stepwise expulsion of neutral [Cp*WO2] units as the main fragmentation process. DFT calculations unveiled the intimate details of the electronic structures of these complexes and fully rationalized the structural and spectroscopic properties.

Mots clés: Tungsten; O ligands; Metal clusters; Density functional calculations

Domaines: Chimie de coordination

Chiara Dinoi, Pelin Sözen, Gülnur Taban, Deniz Demir, Funda Demirhan, et al.. Aqueous Reduction of [Cp*2W2O5]: Characterization of the Triangular Clusters [Cp*3W3O4(OH)2]2+ and [Cp*3W3O6]+ – Comparison with Molybdenum. European Journal of Inorganic Chemistry, 2007, 2007 (27), pp.4306-4316. ⟨10.1002/ejic.200700419⟩. ⟨hal-03193935⟩