Please use this identifier to cite or link to this item: http://hdl.handle.net/10397/35781
Title: Ruthenium Porphyrins with axial pi-Conjugated Arylamide and Arylimide Ligands
Authors: Law, SM
Chen, DQ
Chan, SLF 
Guan, XG
Tsui, WM
Huang, JS
Zhu, NY
Che, CM
Keywords: Metal-amide complexes
Metal-imide complexes
N ligands
Porphyrinoids
Ruthenium
Issue Date: 2014
Publisher: Wiley-VCH
Source: Chemistry - a European journal, 2014, v. 20, no. 35, p. 11035-11047 How to cite?
Journal: Chemistry - a European journal 
Abstract: A series of ruthenium porphyrins [Ru-IV(por)(NHY)(2)] and [Ru-VI(por)(NY)(2)] bearing axially coordinated pi-conjugated arylamide and arylimide ligands, respectively, have been synthesized. The crystal structures of [Ru-IV(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)angstrom, respectively. [Ru-IV(tmp)(NH{Ar<^>Ar})(2)] is an example of metalloporphyrins that bind an arylamide ligand featuring a co-planar biphenyl unit. The [Ru-IV(por)(NHY)(2)] complexes show a quasi-reversible reduction couple or irreversible reduction wave attributed to Ru-IV -> Ru-III with E-pc from -1.06 to -1.40 V versus Cp2Fe+/0 and an irreversible oxidation wave with E-pa from -0.04 to 0.19 V versus Cp2Fe+/0. Reaction of the [Ru-IV(por)(NHY)(2)] with bromine afforded [Ru-IV(por)(NHY)Br]. PhI(OAc)(2) oxidation of the [Ru-IV(por)(NHY)(2)] gave [Ru-VI(por)(NY)(2)]; the latter can be prepared from reaction of [Ru-II(por)(CO)] with aryl azides N3Y. The crystal structure of [Ru-VI(tmp)(N{Ar-Ar-p-OMe})(2)] features Ru-N(arylimide) distances of 1.824(5) and 1.829(5)angstrom. Alkene aziridination and C-H amination catalyzed by "[Ru-II(tmp)(CO)]+ pi-conjugated aryl azides", or mediated by [Ru-VI(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 [Ru-VI(por)(NY)(2)] was examined by DFT calculations.
URI: http://hdl.handle.net/10397/35781
ISSN: 0947-6539 (print)
1521-3765 (online)
DOI: 10.1002/chem.201305084
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