Group ib organometallic chemistry. XXXIV. Thermal behaviour and chemical reactivity of tetranuclear Me2N-substituted diarypropenylcopper-copper anion (Vi2Cu4X2) and mixed diarylpropenyl/organocopper (Vi2Cu4R2) compounds

Abstract

Thermal decomposition of configurationally pure 1,2-diarylpropenylcopper compounds Z-Vi2CU4Br2 and Z-Vi2Cu4R2 [Vi = (2-Me2NC6H4)C=C(Me)-(C6H4Me-4), R = 2-Me2NC6H4 or 4-MeC6H4CC] predominantly results in the formation of ViH. In contrast, only dimers (ViVi) were formed on thermolysis of (Z-ViCu2OTf)η which is a further illustration of the influence of the counter anion on the reactivity of organocopper cluster compounds. However, in both cases partial inversion of configuration, giving mixtures of isomers, was observed. The thermolysis of (Z-ViCu2OTf)η is discussed in terms of OTf-enhanced intraaggregate electron-transfer processes. The formation of incipient vinyl cations which are η2-coordinated to the copper cluster can explain the observed isomerization.

Also in the hydrolysis reaction of Z-Vi2Cu4Br2 mixtures of isomeric ViH compounds were obtained, the E/Z ratio being dependent on the type of reagent used. Mixtures of isomeric ViX compounds (X = Br, Cl, I) were formed in the reaction of Z-Vi2Cu4Br2 with I2 and CuCl2. An explanation for the occurrence of isomerization is presented.

Dimers (ViVi) were almost absent in the product mixture resulting from the reaction of Z-Vi2Cu4Br2 with CuCl2. In contrast, ViVi is obtained in about 50% yield from the reaction of ViLi with CuCl2 which is in accord with earlier observations for the reaction of aryllithium compounds with cupric halides.

Highly selective E-ViBr formation was observed in the reaction of E-ViLi with AgBr. This reaction probably proceeds via a thermally unstable Z-ViAg2Br intermediate.