Rhenium Tricarbonyl Complexes of Azodicarboxylate Ligands.

The excellent π-accepting azodicarboxylic esters adcOR (R = Et, i Pr, t Bu, Bn (CH 2 -C 6 H 5 ) and Ph) and the piperidinyl amide derivative adcpip were used as bridging chelate ligands in dinuclear Re(CO) 3 complexes [{Re(CO) 3 Cl} 2 (µ-adcOR)] and [{Re(CO) 3 Cl} 2 (µ-adcpip)]. From the adcpip ligand the mononuclear derivatives [Re(CO) 3 Cl(adcpip)] and [Re(CO) 3 (PPh 3 )(µ-adcpip)]Cl were also obtained. Optimised geometries from density functional theory (DFT) calculations show syn and anti isomers for the dinuclear fac -Re(CO) 3 complexes at slightly different energies but they were not distinguishable from experimental IR or UV-Vis absorption spectroscopy. The electrochemistry of the adc complexes showed reduction potentials slightly below 0.0 V vs. the ferrocene/ferrocenium couple. Attempts to generate the radicals [{Re(CO) 3 Cl} 2 (µ-adcOR)] •- failed as they are inherently unstable, losing very probably first the Cl - coligand and then rapidly cleaving one [Re(CO) 3 ] fragment. Consequently, we found signals in EPR very probably due to mononuclear radical complexes [Re(CO) 3 (solv)(adc)] • . The underlying Cl - →solvent exchange was modelled for the mononuclear [Re(CO) 3 Cl(adcpip)] using DFT calculations and showed a markedly enhanced Re-Cl labilisation for the reduced compared with the neutral complex. Both the easy reduction with potentials ranging roughly from -0.2 to -0.1 V for the adc ligands and the low-energy NIR absorptions in the 700 to 850 nm range place the adc ligands with their lowest-lying π* orbital being localised on the azo function, amongst comparable bridging chelate N^N coordinating ligands with low-lying π* orbitals of central azo, tetrazine or pyrazine functions. Comparative (TD)DFT-calculations on the Re(CO) 3 Cl complexes of the adcpip ligand using the quite established basis set and functionals M06-2X/def2TZVP/LANL2DZ/CPCM(THF) and the more advanced TPSSh/def2-TZVP(+def2-ECP for Re)/CPCMC(THF) for single-point calculations with BP86/def2-TZVP(+def2-ECP for Re)/CPCMC(THF) optimised geometries showed a markedly better agreement of the latter with the experimental XRD, IR and UV-Vis absorption data.