High oxidation state aqueous organometallics: synthesis and structure of a dinuclear oxo(pentamethylcyclopentadienyl)acetato complex of molybdenum(IV), [Cp*Mo(μ-O)(μ-O2CCH3)]2

Funda Demirhan (1) , Philippe Richard (1) , Rinaldo Poli (1)

1 LSEO - Laboratoire de Synthèse et Electrosynthèse Organométalliques

The zinc reduction of Cp*2Mo2O5 in a MeOH–H2O mixture in the presence of acetic acid affords the diamagnetic dinuclear compound [Cp*MoO(O2CCH3)]2. An X-ray structural investigation reveals a novel dioxo- and diacetato-bridged structure, with a relatively strong metal–metal bond [2.5524(3) Å]. The compound exhibits a reversible one-electron oxidation process in the cyclic voltammogram. A comparison with other related structures reveals the effect of the electric charge on the mononuclear or dinuclear structural choice. Zinc reduction of Cp*2Mo2O5 in water–methanol in the presence of acetic acid affords compound Cp*2Mo2O2(O2CCH3)2, whose dinuclar tetrabridged structure is revealed by an X-ray crystallographic study.

Mots clés: Aqueous organometallic chemistry; Molybdenum; Half-sandwich complexes; Metal–metal bonding; Oxo ligands

Domaines: Chimie de coordination; Cristallographie

Funda Demirhan, Philippe Richard, Rinaldo Poli. High oxidation state aqueous organometallics: synthesis and structure of a dinuclear oxo(pentamethylcyclopentadienyl)acetato complex of molybdenum(IV), [Cp*Mo(μ-O)(μ-O2CCH3)]2. Inorganica Chimica Acta, 2003, 347, pp.61-66. ⟨10.1016/S0020-1693(02)01439-1⟩. ⟨hal-03283678⟩