TY - JOUR
T1 - Electron Transfer and Geometric Conversion of Co-NO Moiety in Saddled Porphyrins
T2 - Implications for Trigger Role of Tetrapyrrole Distortion
AU - Tang, Min
AU - Yang, Yan
AU - Zhang, Shaowei
AU - Chen, Jiafu
AU - Zhang, Jian
AU - Zhou, Zaichun
AU - Liu, Qiuhua
N1 - Funding Information:
*E-mail: [email protected]. *E-mail: [email protected]. ORCID Jian Zhang: 0000-0003-0274-0814 Zaichun Zhou: 0000-0003-2075-8241 Funding This study was supported by the National Natural Science Foundation of China (No. 21372069 and 21602054) and the Scientific Research Fund of Hunan Provincial Education Department (No. 15K042). Notes The authors declare no competing financial interest.
Funding Information:
China Scholarship Council (201708430033) is acknowledged.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2018/1/2
Y1 - 2018/1/2
N2 - The electrons of NO and Co are strongly delocalized in normal {Co-NO}8 species. In this work, {Co-NO}8 complexes are induced to convert from (CoII)+•-NO• to CoIII-NO- by a core contraction of 0.06 Å in saddled cobalt(II) porphyrins. This intramolecular electron transfer mechanism indicates that nonplanarity of porphyrin is involved in driving conversion of the NO units from electrophilic NO• as a bent geometry to nucleophilic NO- as a linear geometry. This implies that distortion acts as a trigger in enzymes containing tetrapyrrole. The electronic behaviors of the CoII ions and Co-NO moieties were confirmed by X-ray crystallography, EPR spectroscopy, theoretical calculation, UV-vis and IR spectroscopy, and electrochemistry.
AB - The electrons of NO and Co are strongly delocalized in normal {Co-NO}8 species. In this work, {Co-NO}8 complexes are induced to convert from (CoII)+•-NO• to CoIII-NO- by a core contraction of 0.06 Å in saddled cobalt(II) porphyrins. This intramolecular electron transfer mechanism indicates that nonplanarity of porphyrin is involved in driving conversion of the NO units from electrophilic NO• as a bent geometry to nucleophilic NO- as a linear geometry. This implies that distortion acts as a trigger in enzymes containing tetrapyrrole. The electronic behaviors of the CoII ions and Co-NO moieties were confirmed by X-ray crystallography, EPR spectroscopy, theoretical calculation, UV-vis and IR spectroscopy, and electrochemistry.
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U2 - 10.1021/acs.inorgchem.7b02455
DO - 10.1021/acs.inorgchem.7b02455
M3 - Article
C2 - 29257677
AN - SCOPUS:85040028192
SN - 0020-1669
VL - 57
SP - 277
EP - 287
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 1
ER -