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Two Discrete RuCp* (Cp*=Pentamethylcyclopentadienyl) Binding Modes of N‐Confused Porphyrins: Peripheral π Complex and Sitting Atop Ruthenocenophane Complex by Skeletal Transformation
Author(s) -
Yamamoto Takaaki,
Mitsuno Koki,
Mori Shigeki,
Itoyama Shuhei,
Shiota Yoshihito,
Yoshizawa Kazunari,
Ishida Masatoshi,
Furuta Hiroyuki
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201801237
Subject(s) - chemistry , porphyrin , ligand (biochemistry) , ruthenium , aryl , stereochemistry , crystallography , medicinal chemistry , photochemistry , catalysis , receptor , organic chemistry , biochemistry , alkyl
Complexation of a RuCp* cation with N‐confused tetraarylporphyrins (NCPs) forms directly bound ruthenium(II) pentamethylcyclopentadienyl (Cp*) π‐complex on a specific meso ‐aryl group (e.g., phenyl) neighboring peripheral imino nitrogen of NCPs in high yields. In contrast, in the case of NCPs bearing bulky meso ‐substituents (e.g., 3,5‐di‐tert‐butylphenyl), new ruthenocenophane‐like complex embedded on an N‐confused calix[4]phyrin was formed through multiple C−H bond activation of methyl groups of Cp* ligand. The mechanistic insight into the formation of the ruthenocenophane was derived from DFT calculations.