1-Zirconacyclobuta-2,3-dienes: synthesis of organometallic analogs of elusive 1,2-cyclobutadiene, unprecedented intramolecular C-H activation, and reactivity studies.
Xinzhe ShiSihan LiMelanie ReißAnke SpannenbergThorsten Holtrichter-RößmannFabian ReißTorsten BeweriesPublished in: Chemical science (2021)
The structure, bonding, and reactivity of small, highly unsaturated ring systems is of fundamental interest for inorganic and organic chemistry. Four-membered metallacyclobuta-2,3-dienes, also referred to as metallacycloallenes, are among the most exotic examples for ring systems as these represent organometallic analogs of 1,2-cyclobutadiene, the smallest cyclic allene. Herein, the synthesis of the first examples of 1-zirconacyclobuta-2,3-dienes of the type [Cp' 2 Zr(Me 3 SiC 3 SiMe 3 )] (Cp' 2 = rac -(ebthi), (ebthi = 1,2-ethylene-1,1'-bis(η 5 -tetrahydroindenyl)) (2a); rac -Me 2 Si(thi) 2 , thi = (η 5 -tetrahydroindenyl), (2b)) is presented. Both complexes undergo selective thermal C-H activation at the 7-position of the ansa -cyclopentadienyl ligand to produce a new type of "tucked-in" zirconocene system, 3a and 3b, that possesses a η 3 -propargyl/allenyl ligand. Both types of complexes react with carbonyl compounds, producing enynes in the case of 2a and 2b, as well as η 1 -allenyl complexes for 3a and 3b. Computational analysis of the structure and bonding of 2a and 3a reveals significant differences to a previously described related Ti complex. All complexes were fully characterised, including X-ray crystallography and experimental results were supported by DFT analysis.