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Updated: Oct 3, 2026

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
Variable Reduction Sequences for Axial (L) and Chelate Ligands (NwedgeN) in Rhenium(I) Complexes
Sascha Berger1, Axel Klein, Wolfgang Kaim
1J. Heyrovsky Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejskova 3, CZ-18223 Prague, Czech Republic.
Abstract:
The rhenium(I) compounds [(NwedgeN)Re(CO)(3)(MQ)](PF(6))(2) (NwedgeN = 2,2'-bipyridine (bpy), 2,2'-bipyrimidine (bpym), 3,3'-bipyridazine (bpdz), or 1,4,7,10-tetraazaphenanthrene (tap) and MQ(+) = N-methyl-4,4'-bipyridinium) undergo four one-electron reduction steps which could be analyzed using cyclic voltammetry, EPR, IR, and UV/vis spectroelectrochemistry. Due to the rather low-lying pi orbital of tap, the corresponding compound shows electron uptake by NwedgeN each time before MQ(+) is reduced. The opposite is observed for the complexes of the other chelate ligands NwedgeN, however, and the pi(NwedgeN) orbital aproaches the pi(MQ(+)) level in the order bpy < bpym < bpdz. Remarkably, the reduction processes of MQ(+) and bpdz in [(bpdz)Re(CO)(3)(MQ)](PF(6))(2) are separated by only 74 mV as deduced from IR spectroelectrochemical analysis. On reduction of the related compound [(bpy)Re(CO)(3)(mpz)](PF(6))(2) (mpz(+) = N-methylpyrazinium), the first two electrons are added to the axial ligand which has a lower-lying pi orbital than MQ(+) and cannot undergo intramolecular twisting.
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