Immobilisation of Iron Porphyrin from an Equilibrium Solution with Diazonium‐Functionalised Axial Ligand: Dependence of Film Composition on Grafting Potential

2021 ◽  
Author(s):  
Alison Downard ◽  
Ting Wu ◽  
Paula A. Brooksby ◽  
Christopher M. Fitchett
Keyword(s):  
Equilibrium Solution ◽  
Axial Ligand ◽  
Iron Porphyrin ◽  
Film Composition

Stable Iron Porphyrin Intramolecularly Coordinated by Alcoholate Anion: Synthesis and Evaluation of Axial Ligand Effect of Alcoholate on Spectroscopy and Catalytic Activity

2019 ◽  
Vol 58 (7) ◽  
pp. 4268-4274
Author(s):  
Yoshinori Shirakawa ◽  
Yuuki Yano ◽  
Yuki Niwa ◽  
Kanako Inabe ◽  
Naoki Umezawa ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Axial Ligand ◽  
Iron Porphyrin ◽  
Ligand Effect

scholarly journals Multireference Ground and Excited State Electronic Structures of Free- versus Iron Porphyrin-Carbenes

2019 ◽  
Author(s):  
Gautam Stroscio ◽  
Martin Srnec ◽  
Ryan Hadt
Keyword(s):  
Excited State ◽  
Potential Energy Surfaces ◽  
Density Functional ◽  
Closed Shell ◽  
Axial Ligand ◽  
Iron Porphyrin ◽  
Functional Theory ◽  
Reaction Coordinates ◽  
Ligand Charge Transfer ◽  
Energy Surfaces

Iron porphyrin carbenes (IPCs) are important reaction intermediates in engineered carbene transferase enzymes and homogeneous catalysis. However, discrepancies between theory and experiment complicate the understanding of IPC electronic structure (i.e., open- vs. closed-shell singlet (OSS vs. CSS)). Here we investigate the structurally dependent ground and excited spin state energetics of a free carbene and its IPC analogs. Only multireference <i>ab initio</i> wave function methods are consistent with experiment and predict a CSS ground state (Fe(II)←{:C(X)Y}<sup>0</sup>), contrary to density functional theory (DFT). The OSS is a high-lying metal-to-ligand charge transfer (MLCT) excited state that is sensitive to the nature of the axial ligand. Furthermore, potential energy surfaces (PESs) along the Fe–C bond elongation coordinate exhibit strong mixings between CSS/OSS characters, which can be an important feature for describing reaction mechanisms. Future studies on IPC reaction coordinates should evaluate contributions from ground and excited state multireference character. <br>

Synthesis and Characterization of an Iron Porphyrin with a Thiolate Axial Ligand and Its Dioxygen Adduct as a Model for the Active Center of Cytochrome P-450

1999 ◽  
Vol 28 (8) ◽  
pp. 729-730 ◽  
Author(s):  
Fumito Tani ◽  
Shinya Nakayama ◽  
Mari Ichimura ◽  
Nobuhumi Nakamura ◽  
Yoshinori Naruta
Keyword(s):  
Active Center ◽  
Axial Ligand ◽  
Synthesis And Characterization ◽  
Iron Porphyrin ◽  
Cytochrome P 450

scholarly journals Multireference Ground and Excited State Electronic Structures of Free- versus Iron Porphyrin-Carbenes

2019 ◽  
Author(s):  
Gautam Stroscio ◽  
Martin Srnec ◽  
Ryan Hadt
Keyword(s):  
Excited State ◽  
Potential Energy Surfaces ◽  
Density Functional ◽  
Closed Shell ◽  
Axial Ligand ◽  
Iron Porphyrin ◽  
Functional Theory ◽  
Reaction Coordinates ◽  
Ligand Charge Transfer ◽  
Energy Surfaces

Iron porphyrin carbenes (IPCs) are important reaction intermediates in engineered carbene transferase enzymes and homogeneous catalysis. However, discrepancies between theory and experiment complicate the understanding of IPC electronic structure (i.e., open- vs. closed-shell singlet (OSS vs. CSS)). Here we investigate the structurally dependent ground and excited spin state energetics of a free carbene and its IPC analogs. Only multireference <i>ab initio</i> wave function methods are consistent with experiment and predict a CSS ground state (Fe(II)←{:C(X)Y}<sup>0</sup>), contrary to density functional theory (DFT). The OSS is a high-lying metal-to-ligand charge transfer (MLCT) excited state that is sensitive to the nature of the axial ligand. Furthermore, potential energy surfaces (PESs) along the Fe–C bond elongation coordinate exhibit strong mixings between CSS/OSS characters, which can be an important feature for describing reaction mechanisms. Future studies on IPC reaction coordinates should evaluate contributions from ground and excited state multireference character. <br>

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