PUB - Publikationen an der Universität Bielefeld

The heterocycles [([eta (1)-Cp*)GaN(Dipp)CH=CHN(Dipp)] (1) and [(eta (1)-Cp*)GaN(Dep)CH= CHN(Dep)] (2) were obtained by oxidative addition of (eta (5)-pentamethylcyclopentadienyl)gallium(I) (Cp*Ga) to Dipp-DAB (1,4-bis(2,6-diisopropylphenyl)-1,4-diazabuta-1,3-diene) and Dep-DAB (1,4-bis(2,6-diethylphenyl)-1,6diazabuta-1,3-diene), respectively. Compounds 1 and 2 are the first examples of monomeric gallium-containing heterocycles of the diazabutadiene (DAB) type. 1 was structurally characterized by X-ray crystallography. In contrast, the reaction of Cp*Ga with But-DAB (1,4-di-tert-butyl-1,4-diazabuta-1,3-diene) led to the formation of the known radical (Ga[Bu-t-DAB](2)) (3) in high yield, thus providing an alternative synthesis to the cocondensation technique used previously. Radical 3 was further characterized by H-1 NMR spectroscopy and cyclic voltammetric studies, which revealed two reversible oxidation steps and one reversible reduction step.