Targeting Ru(III) and Ru(I) η2-alkyne species, 2,2'-(iPr2E)2-substituted diphenylacetylenes (1-E, E = P, As) were em-ployed for the pre-paration of [ECCE]-coordinated ruthenium com-plexes. The re-actions between 1-E and cis-(MeCN)2(COD)RuCl2 led to the required Ru(II) starting materials cis-[ECCE]RuCl2(MeCN) (3-E). Upon oxi-dation of 3-E with PhICl2, the Ru(III) target com-plexes [ECCE]RuCl3 (7-E) were detectable for E = P and E = As, but only the arsa-deriva-tive 7-As was obtained in a …