Electronic Configuration and Ligand Nature of Five-Coordinate Iron Porphyrin Carbene Complexes: An Experimental Study

doi:10.1021/jacs.7b01722

	Electronic Configuration and Ligand Nature of Five-Coordinate Iron Porphyrin Carbene Complexes: An Experimental Study
	Zhang, J; Fuller, W; Schulz, CE; Li, JF; Zhang J(张静); Liu, YL; Xu, W
刊名	JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
	2017
卷号	139 期号:14 页码:5023-5026
ISSN号	0002-7863
DOI	10.1021/jacs.7b01722
文献子类	Article
英文摘要	The five-coordinate iron porphyrin carbene complexes [Fe(TPP) (CCl2)] (TPP = tetraphenylporphyrin), [Fe(TTP) (CCl2)] (TTP = tetratolylporphyrin) and [Fe(TFPP) (CPh2)] (TFPP = tetra(pentafluoro-phenyl)porphyrin), utilizing two types of carbene ligands (CCl2 and CPh2), have been investigated by single crystal X-ray, XANES (X-ray absorption near edge spectroscopy), Mossbauer, NMR and UV-vis spectroscopies. The XANES suggested the iron(II) oxidation state of the complexes. The multitemperature and high magnetic field Mossbauer experiments, which show very large quadrupole splittings (QS, Delta E-Q), determined the S = 0 electronic configuration. More importantly, combined structural and Mossbauer studies, especially the comparison with the low spin iron(II) porphyrin complexes with strong diatomic ligands (CS, CO and CN-) revealed the covalent bond nature of the carbene ligands. A correlation between the iron isomer shifts (IS, delta) and the axial bond distances is established for the first time for these donor carbon ligands (:C-R).
WOS关键词	METAL-ORGANIC FRAMEWORK ; PICKET-FENCE PORPHYRINS ; MOSSBAUER-SPECTROSCOPY ; MOLECULAR-STRUCTURE ; AXIAL LIGAND ; CYTOCHROME-P-450 ; HEMOPROTEINS ; CRYSTAL ; REACTIVITY ; OXIDATION
WOS研究方向	Chemistry
语种	英语
WOS记录号	WOS:000399353800011
内容类型	期刊论文
源URL	[http://ir.ihep.ac.cn/handle/311005/285192]
专题	高能物理研究所_多学科研究中心
作者单位	中国科学院高能物理研究所
推荐引用方式 GB/T 7714	Zhang, J,Fuller, W,Schulz, CE,et al. Electronic Configuration and Ligand Nature of Five-Coordinate Iron Porphyrin Carbene Complexes: An Experimental Study[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2017,139(14):5023-5026.
APA	Zhang, J.,Fuller, W.,Schulz, CE.,Li, JF.,张静.,...&Xu, W.(2017).Electronic Configuration and Ligand Nature of Five-Coordinate Iron Porphyrin Carbene Complexes: An Experimental Study.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,139(14),5023-5026.
MLA	Zhang, J,et al."Electronic Configuration and Ligand Nature of Five-Coordinate Iron Porphyrin Carbene Complexes: An Experimental Study".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 139.14(2017):5023-5026.