Structural and electronic effects in the metalation of porphyrinoids. Theory and experiment.
The structure-reactivity relationships in metalation reactions of porphyrinoids have been studied using experimental and theoretical methods. A series of eight porphyrinoic ligands, derivatives of chlorophylls, was prepared in which both the peripheral groups and the degrees of saturation of the macrocycle were systematically varied. To reveal the solvent and structural factors which control the interactions of these macroligands with metal centers, their interactions with reactive Zn(2+) and inert Pt(2+) ions were investigated using absorption spectroscopy. In parallel, quantum chemical calculations (density functional theory, DFT) were performed for the same set of molecules to examine the influence of structural and electronic factors on the energy of the frontier orbitals, the nucleophilicity/electronegativity of the macrocycle, its hardness, and conformation. These static descriptors of chemical reactivity, relevant to metalation reactions, were verified against the results obtained in the experimental model. The experimentally obtained kinetic data clearly show that the solvent has a crucial role in the activation of the incoming metal center. In terms of chelator structure, the largest effects concern the size of the delocalized pi-electron system and the presence of side groups. Both the DFT calculations and experimental results show the strong influence of the macrocycle rigidity and of the peripheral groups on the chelating ability of porphyrinoids. In particular, the peripheral functionalization of the macrocyclic system seems to drastically reduce its reactivity toward metal ions. The effect of peripheral groups is two-fold: (i) a lower electron density on the core nitrogens, and (ii) increased rigidity of the macrocycle. The outcomes of the theoretical and experimental analyses are discussed also in terms of their relevance to the mechanism of biological metal insertion in the biosynthesis of heme and chlorophyll.
Orzeł
Łukasz
Ł
Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków, Poland.
Kania
Agnieszka
A
Rutkowska-Zbik
Dorota
D
Susz
Anna
A
Stochel
Grazyna
G
Fiedor
Leszek
L
D000097:Acetonitriles / Q000737:chemistry; D002614:Chelating Agents / Q000737:chemistry; D002734:Chlorophyll / Q000737:chemistry; D004583:Electrons; D007700:Kinetics; D008024:Ligands; D008665:Metalloporphyrins / Q000737:chemistry*; D008670:Metals / Q000737:chemistry*; D000432:Methanol / Q000737:chemistry; D010984:Platinum / Q000737:chemistry; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry; D013329:Structure-Activity Relationship; D015032:Zinc / Q000737:chemistry
D000097:Acetonitriles; D002614:Chelating Agents; D008024:Ligands; D008665:Metalloporphyrins; D008670:Metals; D012997:Solvents; D002734:Chlorophyll; D010984:Platinum; D015032:Zinc; D000432:Methanol; C032159:acetonitrile