Crystal-to-Crystal Oxidative Deprotonation of a Di(μ-hydroxo) to a Di(μ-oxo) Dimer of Dimolybdenum Units

A crystal-to-crystal transformation of (DAniF)3Mo2(μ-OH)2Mo2(DAniF)3 (1) to (DAniF)3Mo2(μ-O)2Mo2(DAniF)3 (2), where DAniF is the anion (p-anisyl)NC(H)N(p-anisyl), by dioxygen provides rare insight into the deprotonation process effected by dioxygen. In this dimolybdenum system, the conversion occurs without significant loss of crystallinity. Although no intermediates have been directly observed, a compound containing the [(DAniF)3Mo2(μ-OH)(μ-O)Mo2(DAniF)3]+ cation, a proposed intermediate, has been obtained independently. Possible pathways for the overall conversion of 1 to 2 are discussed.