Synthesis, characterization and structure of thiolate-bridged diruthenium and iron-ruthenium complexes with isocyanide ligands

Interaction of the mixed-valent iron-ruthenium heterodinuclear precursor [Cp*Fe(mu-eta(2):eta(4)-bdt)RuCp*][PF6] Cp* = eta(5)-(CMe5)-Me-5, bdt = benzene-1,2-dithiolate) with isocyanides resulted in coordination activation to give several thiolate-bridged iron-ruthenium complexes bearing isocyanide in excellent yields. Crystallographic analysis clearly reveals the isocyanide ligand is terminally end-on bonded to the iron center and the bdt ligand adopts a rare mu-eta(2):eta(6) coordination mode. Interestingly, when the diruthenium hydride-bridged complex is treated with excess isocyanides, the reductive elimination reaction takes place to afford free Cp*H, meanwhile, six isocyanide molecules supplement the remaining coordination spheres of the diruthenium centers.