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Relevant academic research and scientific papers

Dendrimers with porphyrin cores: Synthetic models for globular heme proteins

Dendritic iron porphyrins were synthesized as functional mimics of globular electron-transfer heme proteins. The cascade molecules 1 · Zn-3 · Zn of first to third generation were obtained starting from the (meso- diarylporphyrin) zinc 6 · Zn which contain

Exploring the Strength of the H-Bond in Synthetic Models for Heme Proteins: The Importance of the N?H Acidity of the Distal Base

The distal hydrogen bond (H-bond) in dioxygen-binding proteins is crucial for the discrimination of O2with respect to CO or NO. We report the preparation and characterization of a series of ZnIIporphyrins, with one of three meso-phenyl rings bearing both an alkyl-tethered proximal imidazole ligand and a heterocyclic distal H-bond donor connected by a rigid acetylene spacer. Previously, we had validated the corresponding CoIIcomplexes as synthetic model systems for dioxygen-binding heme proteins and demonstrated the structural requirements for proper distal H-bonding to CoII-bound dioxygen. Here, we systematically vary the H-bond donor ability of the distal heterocycles, as predicted based on pKavalues. The H-bond in the dioxygen adducts of the CoIIporphyrins was directly measured by Q-band Davies-ENDOR spectroscopy. It was shown that the strength of the hyperfine coupling between the dioxygen radical and the distal H-atom increases with enhanced acidity of the H-bond donor.

Synthesis of dendritic metalloporphyrins with distal H-bond donors as model systems for hemoglobin

We report the synthesis of the first- (G1) and second-generation (G2) dendritic FeII porphyrins 1-Fe-4-Fe (G1) and 6 · Fe (G2) bearing distal H-bond donors ideally positioned for stabilization of Fe II-O2 adducts by H-bonding (Fig. 1). A first approach towards the construction of these novel biomimetic systems failed unexpectedly: the Suzuki cross-coupling between appropriately functionalized ZnII porphyrins and orthoethynylated aryl derivatives, serving as anchors for the distal H-bond donor moieties, was unsuccessful (Schemes 1, 3, and 5), presumably due to steric hindrance resulting from unfavorable coordination of the ethynyl residue to the Pd species in the catalytic cycle (Scheme 6). The target molecules were finally prepared by a route in which the ortho-ethynylated meso-aryl ring is introduced during porphyrin construction in a mixed condensation involving the two dipyrrylmethanes 33 and 34, and aldehyde 36 (Schemes 7 and 8). Following attachment of the dendrons (Scheme 11), the distal H-bond donors were introduced by Sonogashira cross-coupling (Scheme 12), and subsequent metallation afforded the dendritic FeII porphyrins 1 · Fe-6 · Fe. 1H-NMR Spectroscopy proved the location of the H-bond donor moiety atop the porphyrin surface, and X-ray crystal-structure analysis of model system 45 (Fig. 2} revealed that this moiety would not sterically interfere with gas binding. With 1,2-dimethyl-1H-imidazole (DiMeIm) as ligand, the dendritic FeII porphyrins formed five-coordinate high-spin complexes (Figs. 3 and 4) and addition of CO led reversibly to the corresponding stable six-coordinate gas complexes (Fig. 6). Oxygenation, however, did not result in defined FeII-O2 complexes as rapid decomposition to FeIII species took place immediately, even in the case of the G2 dendrimer 6·Fe(DiMeIm) (Fig. 7). In contrast, stable gas adducts are formed between dendritic CoII porphyrins and O 2 in the presence of DiMeIm as axial ligand, as revealed by electron paramagnetic resonance (EPR). The possible stabilization of these complexes through H-bonding involving the distal ligand is currently under investigation in multidimensional and multifrequency pulse EPR experiments.