TY - JOUR
T1 - Characterization of one-electron oxidized copper(ii)-salophen-type complexes; Effects of electronic and geometrical structures on reactivities
AU - Asami, Kazutaka
AU - Takashina, Akiko
AU - Kobayashi, Misato
AU - Iwatsuki, Satoshi
AU - Yajima, Tatsuo
AU - Kochem, Amélie
AU - Van Gastel, Maurice
AU - Tani, Fumito
AU - Kohzuma, Takamitsu
AU - Thomas, Fabrice
AU - Shimazaki, Yuichi
N1 - Copyright:
Copyright 2014 Elsevier B.V., All rights reserved.
PY - 2014/2/7
Y1 - 2014/2/7
N2 - One-electron oxidized salophen-type complexes, [Cu(salophen)]+ (H2salophen = N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2- diaminobenzene), and its methoxy derivatives, [Cu(MeO-salophen)]+ and [Cu(salophen-(MeO)2)]+ (H2MeO-salophen = N,N′-bis(3-tert-butyl-5-methoxysalicylidene)-1,2-diaminobenzene, H 2salophen-(MeO)2 = N,N′-bis(3,5-di-tert- butylsalicylidene)-1,2-diamino-4,5-dimethoxybenzene), have been synthesized and structurally characterized, and their reactivities have been investigated. The solid state structures of the one-electron oxidized forms of these complexes suggested that [Cu(salophen)]+ and [Cu(MeO-salophen)]+ can be assigned to relatively localized Cu(ii)-phenoxyl radical complexes, while [Cu(salophen-(MeO)2)]+ is the diiminobenzene radical complex. On the other hand, [Cu(salophen)]+ in solution showed a different electronic structure from that of the solid sample, the radical electron being delocalized over the whole π-conjugated ligand. The reaction of these oxidized complexes with benzyl alcohol has been investigated in the presence of a large excess of substrate, which revealed the difference in the kinetic behavior between the complexes. The mechanisms of the oxidation have been discussed on the basis of the electronic and geometrical structures and the reaction kinetics.
AB - One-electron oxidized salophen-type complexes, [Cu(salophen)]+ (H2salophen = N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2- diaminobenzene), and its methoxy derivatives, [Cu(MeO-salophen)]+ and [Cu(salophen-(MeO)2)]+ (H2MeO-salophen = N,N′-bis(3-tert-butyl-5-methoxysalicylidene)-1,2-diaminobenzene, H 2salophen-(MeO)2 = N,N′-bis(3,5-di-tert- butylsalicylidene)-1,2-diamino-4,5-dimethoxybenzene), have been synthesized and structurally characterized, and their reactivities have been investigated. The solid state structures of the one-electron oxidized forms of these complexes suggested that [Cu(salophen)]+ and [Cu(MeO-salophen)]+ can be assigned to relatively localized Cu(ii)-phenoxyl radical complexes, while [Cu(salophen-(MeO)2)]+ is the diiminobenzene radical complex. On the other hand, [Cu(salophen)]+ in solution showed a different electronic structure from that of the solid sample, the radical electron being delocalized over the whole π-conjugated ligand. The reaction of these oxidized complexes with benzyl alcohol has been investigated in the presence of a large excess of substrate, which revealed the difference in the kinetic behavior between the complexes. The mechanisms of the oxidation have been discussed on the basis of the electronic and geometrical structures and the reaction kinetics.
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U2 - 10.1039/c3dt52338a
DO - 10.1039/c3dt52338a
M3 - Article
C2 - 24302166
AN - SCOPUS:84891364168
VL - 43
SP - 2283
EP - 2293
JO - Dalton Transactions
JF - Dalton Transactions
SN - 1477-9226
IS - 5
ER -