Comparative chemistry of 18-electron Mo(II) and 17-electron Mo(III) compounds containing only carbon-based ligands

Rinaldo Poli (1) , Li-Sheng Wang (2)

1 LSEO - Laboratoire de Synthèse et Electrosynthèse Organométalliques
2 University of Maryland [College Park]

The chemical reactivity of various kinetically stable isomers of compound CpMo(η3-C3H5)(η4-C4H6), 1, and its oxidation product [1]+, as well as the bis-allyl Mo(III) complex CpMo(η3-C3H5)2, 2, and the bis-diene Mo(II) complex [CpMo(η4-C4H6)2]+, 3, is reviewed. The inertness toward isomerization processes of the allyl and butadiene ligands in the Mo(II) complexes has allowed a study of the relative reactivity toward both electrophilic and nucleophilic addition processes as a function of coordination mode. The dependence of various reaction pathways on the metal oxidation state has also been investigated. Of particular interest is the discovery that the electronically unsaturated intermediate of the butadiene isomerization process is more easily accessible for Mo(III) than for Mo(II). This finding might have relevance for the development of paramagnetic molecules with catalytic activity.

Mots clés: Allyl ligands; Butadiene dimerization; Butadiene polymerization; Molybdenum; Paramagnetic organometallics; Reactivity of coordinated ligands

Domaines: Chimie de coordination

Rinaldo Poli, Li-Sheng Wang. Comparative chemistry of 18-electron Mo(II) and 17-electron Mo(III) compounds containing only carbon-based ligands. Coordination Chemistry Reviews, 1998, 178-180, pp.169-189. ⟨10.1016/S0010-8545(98)80121-5⟩. ⟨hal-03310659⟩