TY - JOUR
T1 - Ruthenium porphyrins with axial π-conjugated arylamide and arylimide ligands
AU - Law, Siu Man
AU - Chen, Daqing
AU - Chan, Sharon Lai Fung
AU - Guan, Xiangguo
AU - Tsui, Wai Man
AU - Huang, Jie Sheng
AU - ZHU, Nianyong
AU - Che, Chi Ming
N1 - Copyright:
Copyright 2014 Elsevier B.V., All rights reserved.
PY - 2014/8/25
Y1 - 2014/8/25
N2 - A series of ruthenium porphyrins [RuIV(por)(NHY)2] and [RuVI(por)(NY)2] bearing axially coordinated π-conjugated arylamide and arylimide ligands, respectively, have been synthesized. The crystal structures of [RuIV(tmp)(NHY)2] (tmp=5,10,15,20-tetramesitylporphyrinato(2-)) with Y=4-methoxy-biphenyl-4-yl (Ar-Ar-p-OMe), 4-chloro-biphenyl-4-yl (Ar-Ar-p-Cl), and 9,9-dibutyl-fluoren-2-yl (Ar^Ar) show axial Ru-N(arylamide) distances of 1.978(4), 1.971(6), and 1.985(13) Å, respectively. [RuIV(tmp)(NH{Ar^Ar})2] is an example of metalloporphyrins that bind an arylamide ligand featuring a co-planar biphenyl unit. The [RuIV(por)(NHY)2] complexes show a quasi-reversible reduction couple or irreversible reduction wave attributed to RuIV→RuIII with Epc from -1.06 to -1.40 V versus Cp2Fe+/0 and an irreversible oxidation wave with Epa from -0.04 to 0.19 V versus Cp 2Fe+/0. Reaction of the [RuIV(por)(NHY) 2] with bromine afforded [RuIV(por)(NHY)Br]. PhI(OAc) 2 oxidation of the [RuIV(por)(NHY)2] gave [RuVI(por)(NY)2]; the latter can be prepared from reaction of [RuII(por)(CO)] with aryl azides N3Y. The crystal structure of [RuVI(tmp)(N{Ar-Ar-p-OMe})2] features Ru-N(arylimide) distances of 1.824(5) and 1.829(5) Å. Alkene aziridination and C-H amination catalyzed by "[RuII(tmp)(CO)]+π-conjugated aryl azides", or mediated by [RuVI(por)(NY)2] with Y=biphenyl-4-yl (Ar-Ar) and Ar-Ar-p-Cl, gave aziridines and amines in moderate yields. The electronic structure of [RuVI(por)(NY)2] was examined by DFT calculations.
AB - A series of ruthenium porphyrins [RuIV(por)(NHY)2] and [RuVI(por)(NY)2] bearing axially coordinated π-conjugated arylamide and arylimide ligands, respectively, have been synthesized. The crystal structures of [RuIV(tmp)(NHY)2] (tmp=5,10,15,20-tetramesitylporphyrinato(2-)) with Y=4-methoxy-biphenyl-4-yl (Ar-Ar-p-OMe), 4-chloro-biphenyl-4-yl (Ar-Ar-p-Cl), and 9,9-dibutyl-fluoren-2-yl (Ar^Ar) show axial Ru-N(arylamide) distances of 1.978(4), 1.971(6), and 1.985(13) Å, respectively. [RuIV(tmp)(NH{Ar^Ar})2] is an example of metalloporphyrins that bind an arylamide ligand featuring a co-planar biphenyl unit. The [RuIV(por)(NHY)2] complexes show a quasi-reversible reduction couple or irreversible reduction wave attributed to RuIV→RuIII with Epc from -1.06 to -1.40 V versus Cp2Fe+/0 and an irreversible oxidation wave with Epa from -0.04 to 0.19 V versus Cp 2Fe+/0. Reaction of the [RuIV(por)(NHY) 2] with bromine afforded [RuIV(por)(NHY)Br]. PhI(OAc) 2 oxidation of the [RuIV(por)(NHY)2] gave [RuVI(por)(NY)2]; the latter can be prepared from reaction of [RuII(por)(CO)] with aryl azides N3Y. The crystal structure of [RuVI(tmp)(N{Ar-Ar-p-OMe})2] features Ru-N(arylimide) distances of 1.824(5) and 1.829(5) Å. Alkene aziridination and C-H amination catalyzed by "[RuII(tmp)(CO)]+π-conjugated aryl azides", or mediated by [RuVI(por)(NY)2] with Y=biphenyl-4-yl (Ar-Ar) and Ar-Ar-p-Cl, gave aziridines and amines in moderate yields. The electronic structure of [RuVI(por)(NY)2] was examined by DFT calculations.
KW - metal-amide complexes
KW - metal-imide complexes
KW - N ligands
KW - porphyrinoids
KW - ruthenium
UR - http://www.scopus.com/inward/record.url?scp=84906779402&partnerID=8YFLogxK
U2 - 10.1002/chem.201305084
DO - 10.1002/chem.201305084
M3 - Journal article
AN - SCOPUS:84906779402
SN - 0947-6539
VL - 20
SP - 11035
EP - 11047
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 35
ER -