Metal-induced reductive ring opening of 1,2,4,5-tetrazines: three resulting coordination alternatives, including the new non-innocent 1,2-diiminohydrazido(2-) bridging ligand system

Reaction of 3,6-diaryl-1,2,4,5-tetrazines (aryl = R = phenyl, 2-furyl or 2-thienyl) with 2 equiv of Ru(acac)2(CH3CN)2 results in reductive tetrazine ring opening to yield diruthenium complexes (acac)2Ru(III)(dih-R(2-))Ru(III)(acac)2] bridged by the new 1,2-diiminohydrazido(2-) (dih-R(2-) = HNC(R)NNC(R)NH(2-)) ligands. rac/meso diastereoisomers could be detected and separated for the compounds with R = phenyl and 2-thienyl, all species are diamagnetic and were characterized by 1H NMR spectroscopy. Crystal structure determination of the meso isomers with R = phenyl and 2-thienyl confirmed the 1,2-diiminohydrazido formulation through long N-N (approximately 1.40 A) and short C=N(H) bonds (approximately 1.31 A), implying two bridged ruthenium(III) centers at about 4.765 A distance with strong antiferromagnetic coupling. The complexes undergo two reversible and well-separated one-electron reduction and oxidation processes, respectively. EPR Spectroscopy of the paramagnetic intermediates with comproportionation constants K(c) > 10(12) and UV-vis-NIR spectroelectrochemistry were used to identify the accessible redox states as (acac)2Ru(II)(dih-R(2-))Ru(II)(acac)2]2-, (acac)2Ru(II)(dih-R(*-))Ru(II)(acac)2]-, (acac)2Ru(III)(dih-R(2-))Ru(III)(acac)2], (acac)2Ru(III)(dih-R(*-))Ru(III)(acac)2]+, and (acac)2Ru(III)(dih-R)Ru(III)(acac)2]2+. While the UV-vis-NIR spectroscopic response of (acac)2Ru(dih-R)Ru(acac)2](0/-/2-) is very similar to that of (bpy)2Ru(adc-R)Ru(bpy)2](4+/3+/2+), adc-R(2-) = 1,2-diacylhydrazido(2-), the EPR result indicating ligand-centered spin for (acac)2Ru(II)(dih-R(*-))Ru(II)(acac)2]- despite deceptive NIR absorptions around 1400 nm reveals distinct differences in the electronic structures.