[Lithium tert-butylperoxide]12 : Crystal Structure of an Aggregated Oxenoid.

The X-ray crystal structure of the dodecameric lithium tert-butylperoxide [2]12 is the first of an alkali or alkaline earth peroxide. It shows the lithium ion bridging the two oxygen atoms of the peroxide unit and a slight lenghtening of the O-O bond, in agreement with quantum-chemical calculations. A calculation for the model reaction of MeLi with LiOOH to give MeOLi and LiOH reveals the importance of Li bridging the O-O bond in the transition state of this reaction, as similarly discussed for many oxidation reactions of (transition-) metal peroxides. Preliminary theoretical studies of the O-O bond length (and thus of the oxenoid character) as a function of the aggregation of 2 disclose that increasing aggregation leads to stabilization of the charge at the anionic oxygen atom and thus to a reduction of the O-O bond length (oxenoid character). Related considerations of the effect of aggregation should also be valid for other lithium (organometallic) compounds and their structure and reactivity as well as other properties.