New insight into metalloporphyrin excited state structures and axial ligand binding from X-ray transient absorption spectroscopic studies

Megan L. Shelby; Michael W. Mara; Lin X. Chen

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New insight into metalloporphyrin excited state structures and axial ligand binding from X-ray transient absorption spectroscopic studies

机译：New insight into metalloporphyrin excited state structures and axial ligand binding from X-ray transient absorption spectroscopic studies

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Metalloporphyrin axial ligation is an important process in catalysis and the enzymatic chemistry of proteins and is metal center dependent. Direct structural dynamics measurements on different metal-loporphyrins using X-ray transient absorption spectroscopy (XTA) have brought new insight into this extensively studied process. This review uses two representative open shell metalloporphyrins, nickel tetramesitylporphyrin (NiTMP) and iron protoporphyrin (FePP), to demonstrate the capability of XTA in resolving both electronic and nuclear structures of these porphyrins in axial ligation processes. A surprisingly broad 3d orbital energy level distribution has been related to differences in the conformational distribution of NiTMP in the ground and excited state, which suggests a unified mechanism for axial ligation in open shell metalloporphyrins driven by transient vacancies in the 3d_(_Z2) orbital, which is aligned with the axial ligation coordinate. XTA studies also show that dynamic and structural differences in the CO dissociation process are influenced by the metal site environments, demonstrated by the comparison of FePP in solution and heme in myoglobin. These results imply a porphyrin conformational control of ligation and therefore insight into metalloporphyrin catalyst design involving control the axial ligation/deligation processes as well as deduction of enzymatic regulation of ligand binding.

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《Coordination chemistry reviews》 |2014年第10期|291-299|共9页
作者
Megan L. Shelby; Michael W. Mara; Lin X. Chen;
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作者单位

Department of Chemistry, Northwestern University, Evanston, IL 60208, USA,Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL 60439, USA;

Department of Chemistry, Northwestern University, Evanston, IL 60208, USA;

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收录信息美国《科学引文索引》(SCI);美国《生物学医学文摘》(MEDLINE);
原文格式 PDF
正文语种英语
中图分类无机化学;
关键词
Metalloporphyrins; Photodissociation of the ligand; Hemeproteins; Excited state molecular structures; X-ray transient absorption; Catalysis;

New insight into metalloporphyrin excited state structures and axial ligand binding from X-ray transient absorption spectroscopic studies

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