Ruthenium porphyrins with axial π-conjugated arylamide and arylimide ligands

Siu Man Law; Daqing Chen; Sharon Lai Fung Chan; Xiangguo Guan; Wai Man Tsui; Jie Sheng Huang; Nianyong ZHU; Chi Ming Che

doi:10.1002/chem.201305084

Ruthenium porphyrins with axial π-conjugated arylamide and arylimide ligands

Siu Man Law
, Daqing Chen
, Sharon Lai Fung Chan
, Xiangguo Guan
, Wai Man Tsui
, Jie Sheng Huang
, Nianyong ZHU
, Chi Ming Che^*

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Journal article › peer-review

18 Citations (Scopus)

Abstract

A series of ruthenium porphyrins [Ru^IV(por)(NHY)₂] and [Ru^VI(por)(NY)₂] bearing axially coordinated π-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) Å, 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 Cp ₂Fe^+/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) Å. Alkene aziridination and C-H amination catalyzed by "[Ru^II(tmp)(CO)]+π-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.

Original language	English
Pages (from-to)	11035-11047
Number of pages	13
Journal	Chemistry - A European Journal
Volume	20
Issue number	35
DOIs	https://doi.org/10.1002/chem.201305084
Publication status	Published - 25 Aug 2014

User-Defined Keywords

metal-amide complexes
metal-imide complexes
N ligands
porphyrinoids
ruthenium

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10.1002/chem.201305084

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@article{424034dff0d7475d9f918a66dd02805f,

title = "Ruthenium porphyrins with axial π-conjugated arylamide and arylimide ligands",

abstract = "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\textasciicircum{}Ar) show axial Ru-N(arylamide) distances of 1.978(4), 1.971(6), and 1.985(13) {\AA}, respectively. [RuIV(tmp)(NH\{Ar\textasciicircum{}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) {\AA}. 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.",

keywords = "metal-amide complexes, metal-imide complexes, N ligands, porphyrinoids, ruthenium",

author = "Law, \{Siu Man\} and Daqing Chen and Chan, \{Sharon Lai Fung\} and Xiangguo Guan and Tsui, \{Wai Man\} and Huang, \{Jie Sheng\} and Nianyong ZHU and Che, \{Chi Ming\}",

year = "2014",

month = aug,

day = "25",

doi = "10.1002/chem.201305084",

language = "English",

volume = "20",

pages = "11035--11047",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "John Wiley \& Sons Ltd",

number = "35",

}

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

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 - https://www.scopus.com/pages/publications/84906779402

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 -

Ruthenium porphyrins with axial π-conjugated arylamide and arylimide ligands

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