TY - JOUR
T1 - Organometallic Group 11 (CuIII, AgIII, AuIII) Complexes of a trans-Doubly N-Confused Porphyrin
T2 - An “Expanded Imidazole” Structural Motif
AU - Yan, Jiaying
AU - Yang, Yufeng
AU - Ishida, Masatoshi
AU - Mori, Shigeki
AU - Zhang, Bao
AU - Feng, Yaqing
AU - Furuta, Hiroyuki
N1 - Funding Information:
The work was supported by the Grant-in-Aid (no. 15K13646 to H.F. 16K05700 and 17H05377 (Coordination Asymmetry) to MI) from the Ministry of Education, Culture, Sports, Science and Technology of Japan. The financial support from a bilateral program between JSPS and the National Research Foundation (NRF) of South Africa is also acknowledged. The authors acknowledge to the China Scholarship Council for financial supports, and also thank Prof. Motonori Watanabe (Kyushu University) for allowing access to an NMR spectroscopic instrument.
Publisher Copyright:
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2017/8/22
Y1 - 2017/8/22
N2 - Complexation of group 11 metal cations with an α-bis(phenylthio)-substituted trans-doubly N-confused porphyrin (trans-N2CPSPh: 4) afforded a series of square-planar trivalent organometallic complexes (i.e., Cu-H4, Ag-H4, and Au-H4). The X-ray crystal structures of the complexes revealed highly planar core geometries along with the presence of peripheral amine and imine nitrogen sites of the pyrrolic moieties. NMR, UV/Vis absorption, and magnetic circular dichroism (MCD) spectroscopies suggested the 18 π-electron aromaticity of the complexes. The aromaticity was also fully analyzed by various theoretical methodologies such as nucleus-independent chemical shift (NICS) and anisotropic induced current density (ACID) calculations. The central metal affects the amphiprotic character of the complexes possessing both pyrrolic amino nitrogen and imino nitrogen atoms at the periphery, which was examined by the photometric titration with trifluoroacetic acid (TFA) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), respectively. The inherent acidity of the complexes was followed in the order; Cu-H4>Au-H4>Ag-H4 and that of basicity was Au-H4>Ag-H4>Cu-H4. The complexes could be considered as an “expanded imidazole” structural motif.
AB - Complexation of group 11 metal cations with an α-bis(phenylthio)-substituted trans-doubly N-confused porphyrin (trans-N2CPSPh: 4) afforded a series of square-planar trivalent organometallic complexes (i.e., Cu-H4, Ag-H4, and Au-H4). The X-ray crystal structures of the complexes revealed highly planar core geometries along with the presence of peripheral amine and imine nitrogen sites of the pyrrolic moieties. NMR, UV/Vis absorption, and magnetic circular dichroism (MCD) spectroscopies suggested the 18 π-electron aromaticity of the complexes. The aromaticity was also fully analyzed by various theoretical methodologies such as nucleus-independent chemical shift (NICS) and anisotropic induced current density (ACID) calculations. The central metal affects the amphiprotic character of the complexes possessing both pyrrolic amino nitrogen and imino nitrogen atoms at the periphery, which was examined by the photometric titration with trifluoroacetic acid (TFA) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), respectively. The inherent acidity of the complexes was followed in the order; Cu-H4>Au-H4>Ag-H4 and that of basicity was Au-H4>Ag-H4>Cu-H4. The complexes could be considered as an “expanded imidazole” structural motif.
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U2 - 10.1002/chem.201701958
DO - 10.1002/chem.201701958
M3 - Article
C2 - 28612992
AN - SCOPUS:85026446718
SN - 0947-6539
VL - 23
SP - 11375
EP - 11384
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 47
ER -