A triptycene-based bis(benzimidazole) ester ligand, L3, was designed to enhance the electron donating ability of the heterocyclic nitrogen atoms relative to those of the first generation bis(benzoxazole) analogs, L1 and L2. A convergent synthesis of L3 was designed and executed. Three-component titration experiments using UV-visible spectroscopy revealed that the desired diiron(II) complex could be obtained with a 1:2:1 ratio of L3:Fe(OTf)2(MeCN)2:external carboxylate reactants. X-ray crystallographic studies of two diiron complexes derived in this manner from L3 revealed their formulas to be [Fe2L3(μ-OH)(μ-O2CR)(OTf)2], where R = 2,6-bis(p-tolyl)benzoate (7) or triphenylacetate (8). The structures are similar to that of a diiron complex derived from L1, [Fe2L1(μ-OH)(μ-O2CArTol)(OTf)2] (9) with a notable difference being that, in 7 and 8, the geometry at iron more closely resembles square-pyramidal than trigonal-bipyramidal. Mössbauer spectroscopic analyses of 7 and 8 indicate the presence of high-spin diiron(II) cores. These results demonstrate the importance of substituting benzimidazole for benzoxazole for assembling biomimetic diiron complexes with syn disposition of two N-donor ligands, as found in O2-activating carboxylate-bridged diiron centers in biology.
A triptycene-based bis(benzimidazole) ester ligand, L3, was designed to enhance the electron donating ability of the heterocyclic n class="Chemical">nitrogen atoms relative to those of the first generation bis(benzoxazole) analogs, L1 and L2. A convergent synthesis of L3 was designed and executed. Three-component titration experiments using UV-visible spectroscopy revealed that the desired diiron(II) complex could be obtained with a 1:2:1 ratio of L3:Fe(OTf)2(MeCN)2:external carboxylate reactants. X-ray crystallographic studies of two diiron complexes derived in this manner from L3 revealed their formulas to be [Fe2L3(μ-OH)(μ-O2CR)(OTf)2], where R = 2,6-bis(p-tolyl)benzoate (7) or triphenylacetate (8). The structures are similar to that of a diiron complex derived from L1, [Fe2L1(μ-OH)(μ-O2CArTol)(OTf)2] (9) with a notable difference being that, in 7 and 8, the geometry at iron more closely resembles square-pyramidal than trigonal-bipyramidal. Mössbauer spectroscopic analyses of 7 and 8 indicate the presence of high-spin diiron(II) cores. These results demonstrate the importance of substituting benzimidazole for benzoxazole for assembling biomimetic diiron complexes with syn disposition of two N-donor ligands, as found in O2-activating carboxylate-bridged diiron centers in biology.
Authors: E I Solomon; T C Brunold; M I Davis; J N Kemsley; S K Lee; N Lehnert; F Neese; A J Skulan; Y S Yang; J Zhou Journal: Chem Rev Date: 2000-01-12 Impact factor: 60.622