Abstract
The reactions between arylethynes (either BuLi activated or Et3N assisted) and Ru2(RDMBA)4X2, where RDMBA is either N,N‘-dimethylbenzamidinate (R = H) or N,N‘-dimethyl-m-methoxybenzamidinate (R = m-MeO) and X is either Cl- or NO3-, resulted in the compounds Ru2(RDMBA)4(C⋮CC6H4Y)2 (Y = H (1a,b), 4-NO2 (2a,b), 4-CN (3a,b), 3-CN (4a,b), 4-NMe2 (5a,b); R = H (a), m-MeO (b)). The single-crystal X-ray diffraction study of 1b and 2a revealed the linear alignment of the arylethynyl ligands along the Ru−Ru vector. All of the compounds display two Ru-based one-electron processes, an oxidation and a reduction, and their electrode potentials correlate linearly with the Hammett constants of substituent Y. Compounds 5a,b display an additional pair of one-electron processes attributed to the oxidation of 4-NMe2 groups, on the basis of which an extensive electron delocalization along the metallayne backbone was inferred.
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