0000000001311217
AUTHOR
Eric Van Caemelbecke
Cobalt Corroles with Bis‐Ammonia or Mono‐DMSO Axial Ligands. Electrochemical, Spectroscopic Characterizations and Ligand Binding Properties
International audience; Four bis-ammonia ligated cobalt corroles and four mono-DMSO ligated cobalt corroles with different mesoaryl substituents on the macrocycle (A 2 Band A 3-corroles) were synthesized and investigated as to their electrochemical and spec-troscopic properties under different solution conditions. The complexation energies of the investigated cobalt corroles were theoretically calculated to illustrate the propensity of the cobalt center for pentacoordination or hexa-coordination with various axial ligands (DMSO, CO, py and NH 3). The structure of one hexacoordinate bis-NH 3 cobalt corrole complex was also determined by X-ray diffraction.
Decreased Electron Transfer Rates of Manganese Porphyrins with Conformational Distortion of the Macrocycle
Slow electron transfer to manganese(iii) porphyrins results when the macrocycle deviates from planarity. This was demonstrated by measuring the kinetics of homogeneous electron transfer from a series of semiquinone radical anions to synthetic manganese porphyrins (shown schematically; R1 =H, Cl, F; R2 =H, F). Three of the four porphyrins studied have nonplanar macrocycles. These results could have implications for the role of manganese in biological electron transfer processes.
Migration Reactivities of σ-Bonded Ligands of Organoiron and Organocobalt Porphyrins Depending on Different High Oxidation States
Migration reactivities of sigma-bonded organo-iron and -cobalt porphyrins were examined as a function of the compound oxidation state. Migration rates were determined for both the one-electron and two-electron oxidized species produced in the electron-transfer oxidation with different oxidants in acetonitrile at 298 K. The investigated compounds are represented as [(OETPP)Fe(R)](n)()(+), where n = 1 or 2, OETPP = the dianion of 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetraphenylporphyrin, and R = C(6)H(5), 3,5-C(6)F(2)H(3), or C(6)F(5), and as [(TPP)Co(R)](n)()(+), where n = 1 or 2, TPP = the dianion of 5,10,15,20-tetraphenylporphyrin, and R = CH(3) or C(6)H(5). The rapid two-electron oxid…
Reduzierte Geschwindigkeit des Elektronentransfers bei Mangan-Porphy- rinen mit verzerrter Konformation des Makrocyclus
Ein langsamer Elektronentransfer auf Mangan(III)-Porphyrine ist die Folge, wenn der Porphyrinmakrocyclus nicht planar ist. Dies konnte anhand kinetischer Messungen des homogenen Elektronentransfers von einer Reihe von Semichinon-Radikalanionen auf synthetische Manganporphyrine (siehe Formel, R1 = H, Cl, F; R2 = H, F) gezeigt werden. In drei der vier untersuchten Porphyrine ist der Makrocyclus nicht planar. Dieses Ergebnis konnte fur das Verstandnis der Rolle von Mangan in biologischen Elektronentransferprozessen wichtig sein.
CCDC 1812155: Experimental Crystal Structure Determination
Related Article: Valentin Quesneau, Wenqian Shan, Nicolas Desbois, Stephane Brandes, Yoann Rousselin, Meddy Vanotti, Virginie Blondeau-Patissier, Mario Naitana, Paul Fleurat-Lessard, Eric Van Caemelbecke, Karl M. Kadish, Claude P. Gros|2018|Eur.J.Inorg.Chem.|2018|4265|doi:10.1002/ejic.201800897
CCDC 1815709: Experimental Crystal Structure Determination
Related Article: Valentin Quesneau, Wenqian Shan, Nicolas Desbois, Stephane Brandes, Yoann Rousselin, Meddy Vanotti, Virginie Blondeau-Patissier, Mario Naitana, Paul Fleurat-Lessard, Eric Van Caemelbecke, Karl M. Kadish, Claude P. Gros|2018|Eur.J.Inorg.Chem.|2018|4265|doi:10.1002/ejic.201800897