Synthesis, Characterization, and Reactivity of Multinuclear Zinc(II) Alkyl Derivatives of Linked Phenoxides

Alkyl zinc derivatives of tris(3,5-dialkyl-2-hydroxyphenyl)methanes (alkyl = tert -butyl 1a, methyl 1b, tert -pentyl 1c ) have been prepared by reaction with dimethyl or diethylzinc, and characterized. Whereas dimethylzinc with 1a or diethylzinc with 1b give S 6 symmetric, hexanuclear aggregates with the general formula 1 2 (ZnR) 6 (R = Me 2a, Et 2b ), when 1a reacts with diethylzinc, solvent dependent reactions take place. If dichloromethane is used for the reaction solvent, a dimeric, C 2 symmetric, tetranuclear product with the formula 1a 2 Zn 2 (ZnEt) 2 ( 3 ) is isolated while in diethyl ether, a C 2 symmetric, pentanuclear aggregate 1a 2 Zn(ZnEt) 4 ( 4 ) forms, and in tetrahydrofuran a C 3 symmetric trinuclear compound 1a [ZnEt(THF)] 3 ( 5a ) is produced. Each example is represented by a single-crystal X-ray structure determination. Preliminary studies regarding their activity toward the copolymerization of cyclohexene oxide and carbon dioxide are also reported.