TY - JOUR
T1 - Catalytic and Biocatalytic Iron Porphyrin Carbene Formation
T2 - Effects of Binding Mode, Carbene Substituent, Porphyrin Substituent, and Protein Axial Ligand
AU - Khade, Rahul L.
AU - Zhang, Yong
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015/6/24
Y1 - 2015/6/24
N2 - Iron porphyrin carbenes (IPCs) are important intermediates in various chemical reactions catalyzed by iron porphyrins and engineered heme proteins, as well as in the metabolism of various xenobiotics by cytochrome P450. However, there are no prior theoretical reports to help understand their formation mechanisms and identify key information governing the binding mode, formation feasibility, and stability/reactivity. A systematic quantum chemical study was performed to investigate the effects of carbene substituent, porphyrin substituent, and axial ligand on IPC formation pathways. Results not only are consistent with available experimental data but also provide a number of unprecedented insights into electronic, steric, and H-bonding effects of various structural factors on IPC formation mechanisms. These results shall facilitate research on IPC and related systems for sustainable chemical catalysis and biocatalysis.
AB - Iron porphyrin carbenes (IPCs) are important intermediates in various chemical reactions catalyzed by iron porphyrins and engineered heme proteins, as well as in the metabolism of various xenobiotics by cytochrome P450. However, there are no prior theoretical reports to help understand their formation mechanisms and identify key information governing the binding mode, formation feasibility, and stability/reactivity. A systematic quantum chemical study was performed to investigate the effects of carbene substituent, porphyrin substituent, and axial ligand on IPC formation pathways. Results not only are consistent with available experimental data but also provide a number of unprecedented insights into electronic, steric, and H-bonding effects of various structural factors on IPC formation mechanisms. These results shall facilitate research on IPC and related systems for sustainable chemical catalysis and biocatalysis.
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U2 - 10.1021/jacs.5b03437
DO - 10.1021/jacs.5b03437
M3 - Article
C2 - 26067900
AN - SCOPUS:84935018556
SN - 0002-7863
VL - 137
SP - 7560
EP - 7563
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 24
ER -