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Synthesis and antifreeze activity of fish antifreeze glycoproteins and their analogues

Photodissociation and photoelectron imaging of molecular ions: probing multisurface and multichannel dynamics

Total synthesis of all (−)-agelastatin alkaloids

Exploiting donor–acceptor interactions in aqueous dynamic combinatorial libraries: exploratory studies of simple systems

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Unified synthesis of enantiopure β²h, β³h and β^2,3-amino acids

X-ray snapshots for metalloporphyrin axial ligation

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X-ray snapshots for metalloporphyrin axial ligation

Content Provider	Royal Society of Chemistry (RSC)
Author	Mara, Michael W. Lockard, Jenny V. Attenkofer, Klaus Wasinger, Erik C. Stickrath, Andrew B. Smolentsev, Grigory Chen, Lin X. Zhang, Xiaoyi Jennings, Guy Soldatov, Alexander
Copyright Year	2010
Abstract	Axial ligation mechanisms of a metalloporphyrin, nickel(II) tetramesitylporphyrin (NiTMP), were investigated by static and transient X-ray absorption spectroscopy at Ni K-edge (8.333 keV). A surprisingly broad (i.e. ∼1.4 eV) linewidth for the 1s → 3dx2-y2 transition in the ground state was attributed to strong geometry dependent 3d molecular orbital (MO) energies due to coexisting conformers in solution. The broad distribution of 3d MO energy levels enables transient degeneracy of the 3dz2 and 3dx2-y2 MOs to produce a temporary vacancy in the 3dz2 MO which favors axial ligation. Photoexcitation also induces the vacancy in the 3dz2 MO, leading to a more than two-fold enhancement in the axial ligated species. Therefore, a unified axial ligation mechanism for both the ground and excited state is proposed based on the elucidation of the excited state structural dynamics, which will have a broad impact in understanding and controlling axial ligation in enzymatic reactions and molecular catalysis involving transient axial ligation.
Starting Page	642
Ending Page	650
Page Count	9
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	1
Issue Number	5
Journal	Chemical Science
DOI	10.1039/c0sc00323a
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Molecular orbital Spectroscopy Metal K-edge Covalent bond Electronvolt Nickel Spectral line X-ray absorption spectroscopy Molecular geometry Photoexcitation
Content Type	Text
Resource Type	Article
Subject	Chemistry

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X-ray snapshots for metalloporphyrin axial ligation

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