Abstract: | The Conjugative Bridging of Organometallic Reaction Centers in Heterodinuclear Complexes (OC)3ClRe(μ‐L)MCl(C5Me5)]+, M = Rh or Ir ‐ Spectroscopic Consequences of Reductive Activation Heterodinuclear complexes (OC)3ClRe(μ‐L)MCl(C5Me5)](PF6), M = Rh or Ir and L = 2, 5‐bis(1‐phenyliminoethyl)pyrazine (bpip), 3, 6‐bis(2‐pyridyl)‐1, 2, 4, 5‐tetrazine (bptz) or 2, 2′‐bipyrimidine (bpym), were synthesized via mononuclear rhenium compounds (L)Re(CO)3Cl. The stepwise reductive activation under chloride dissociation was studied through cyclic voltammetry and spectroelectrochemistry in the range of CO stretching vibrations (IR), charge transfer absorptions (UV/Vis) and electron spin resonance (ESR) for paramagnetic intermediates of the mono‐ and heterodinuclear compounds. While complexes of bpip and bptz form one‐electron reduced radical intermediates (OC)3ClRe(μ‐L)MCl(C5Me5)] ˙ , the compounds with bpym react under MCl‐dissociative two‐electron reduction directly to (OC)3ClRe(μ‐L)M(C5Me5)]. |