Seven‐Membered Heterodimetallic Ring Systems from (Conjugated Diene) Group 4 Metallocene Complexes and Organoaluminium Reagents

The ( s‐trans/s‐cis ‐η 4 ‐butadiene)zirconocene reagent adds dimethylaluminium chloride to yield the heterodimetallacyclic main group/transition‐metal system 2b , containing a seven‐membered metallacyclic framework that exhibits a “π‐agostic” s̀‐allyl zirconium interaction. Similar compounds ( 2c–f, 5a, 6 ) are obtained upon reaction of (butadiene)zirconocene with Et 2 All and (butadiene)hafnocene with Me 2 AlCl or Et 2 AlI. Addition of Me 2 AlCl or Et 2 AlI to (isoprene)zirconocene proceeds regioselectively to yield the corresponding heterodimetallacycles bearing the methyl substituent at C‐3 (i.e. near to the attached aluminium center). The iodide‐bridged heterodimetallacycles exhibit dynamic NMR spectra that indicate a rapid enantiomerization process on the NMR time scale (ΔG± ent ≈ 11–12 kcal mol −1 ). It is assumed that this automerization reaction proceeds by rate‐limiting aluminium‐halogen bond cleavage leading to an acyclic mixed metal heterodimetallic intermediate. This process is markedly inhibited by the presence of excess diethylaluminium iodide.