Reported in this contribution are the synthesis and characterization of the following diruthenium arylacetylide compounds containing dialkyl–triazene capping groups: Ru 2 (ap) 4 -(CC-4-C 6 H 4 –N 3 Et 2 ) (2), Ru 2 (ap) 4 -(CC-3-C 6 H 4 –N 3 Et 2 ) (3), and trans-[Ru 2 (DMBA) 4 ](-CC-4-C 6 H 4 –N 3 Et 2 ) 2 (4), where ap is 2-anilinopyridinate and DMBA is N,N-dimethylbenzamidinate. Compounds 2/3 were prepared by the addition of diethylamine to the diazonium intermediate, Ru 2 (ap) 4 -(CC-3/4-C 6 H 4 –N 2 + ), under basic conditions, and compound 4 was synthesized from Ru 2 (DMBA) 4 (NO 3 ) 2 and HCC-4-C 6 H 4 –N 3 Et 2 under weakly basic conditions. An X-ray study of 4 provided a unique structural example of inorganic compounds bearing dialkyl–triazene functional groups, and revealed a minimal alteration in the first coordination sphere of Ru 2 core upon the attachment of dialkyl–triazene caps. Similar to previously reported diruthenium compounds, 2, 3 and 4 display rich redox chemistry with a reversible diruthenium oxidation and reduction, as well as an oxidation of the triazene group to a radical.