Synthesis, structures and reactivity of ruthenium nitrosyl complexes containing Kläui's oxygen tripodal ligand

Ho Fai Ip; Xiao Yi Yi; Wai Yeung WONG; Ian D. Williams; Wa Hung Leung

doi:10.1039/c1dt10306g

Synthesis, structures and reactivity of ruthenium nitrosyl complexes containing Kläui's oxygen tripodal ligand

Ho Fai Ip, Xiao Yi Yi, Wai Yeung WONG, Ian D. Williams, Wa Hung Leung^*

^*Corresponding author for this work

Department of Chemistry

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

13 Citations (Scopus)

Abstract

Ruthenium nitrosyl complexes containing the Kläui's oxgyen tripodal ligand L_OEt^- ([CpCo{P(O)(OEt)₂} ₃]^- where Cp = η⁵-C₅H ₅) were synthesized and their photolysis studied. The treatment of [Ru(NN)(NO)Cl₃] with [AgL_OEt] and Ag(OTf) afforded [L _OEtRu(NN)(NO)][OTf]₂ where NN = 4,4′-di-tert-butyl- 2,2′-bipyridyl (dtbpy) (2·[OTf]₂), 2,2′-bipyridyl (bpy) (3·[OTf]₂), N,N,N′N′- tetramethylethylenediamine (4·[OTf]₂). Anion metathesis of 3·[OTf]₂ with HPF₆ and HBF₄ gave 3·[PF₆]₂ and 3·[BF₄]₂, respectively. Similarly, the PF₆^- salt 4·[PF ₆]₂ was prepared by the reaction of 4·[OTf] ₂ with HPF₆. The irradiation of [L_OEtRu(NO) Cl₂] (1) with UV light in CH₂Cl₂-MeCN and tetrahydrofuran (thf)-H₂O afforded [L_OEtRuCl ₂(MeCN)] (5) and the chloro-bridged dimer [L_OEtRuCl] ₂(μ-Cl)₂ (6), respectively. The photolysis of complex [2][OTf]₂ in MeCN gave [L_OEtRu(dtbpy)(MeCN)][OTf] ₂ (7). Refluxing complex 5 with RNH₂ in thf gave [L _OEtRuCl₂(NH₂R)] (R = tBu (8), p-tol (9), Ph (10)). The oxidation of complex 6 with PhICl₂ gave [L _OEtRuCl₃] (11), whereas the reduction of complex 6 with Zn and NH₄PF₆ in MeCN yielded [L_OEtRu(MeCN) ₃][PF₆] (12). The reaction of 3·[BF ₄]₂ with benzylamine afforded the μ-dinitrogen complex [{L_OEtRu(bpy)}₂(μ-N₂)][BF₄] ₂ (13) that was oxidized by [Cp₂Fe]PF₆ to a mixed valence Ru^II,III species. The formal potentials of the RuL _OEt complexes have been determined by cyclic voltammetry. The structures of complexes 5,6,10,11 and 13 have been established by X-ray crystallography.

Original language	English
Pages (from-to)	11043-11050
Number of pages	8
Journal	Dalton Transactions
Volume	40
Issue number	41
DOIs	https://doi.org/10.1039/c1dt10306g
Publication status	Published - 7 Nov 2011

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Inorganic Chemistry

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@article{6cb90b850e894ef0b9a7a53737258867,

title = "Synthesis, structures and reactivity of ruthenium nitrosyl complexes containing Kl{\"a}ui's oxygen tripodal ligand",

abstract = "Ruthenium nitrosyl complexes containing the Kl{\"a}ui's oxgyen tripodal ligand LOEt- ([CpCo{P(O)(OEt)2} 3]- where Cp = η5-C5H 5) were synthesized and their photolysis studied. The treatment of [Ru(NN)(NO)Cl3] with [AgLOEt] and Ag(OTf) afforded [L OEtRu(NN)(NO)][OTf]2 where NN = 4,4′-di-tert-butyl- 2,2′-bipyridyl (dtbpy) (2·[OTf]2), 2,2′-bipyridyl (bpy) (3·[OTf]2), N,N,N′N′- tetramethylethylenediamine (4·[OTf]2). Anion metathesis of 3·[OTf]2 with HPF6 and HBF4 gave 3·[PF6]2 and 3·[BF4]2, respectively. Similarly, the PF6- salt 4·[PF 6]2 was prepared by the reaction of 4·[OTf] 2 with HPF6. The irradiation of [LOEtRu(NO) Cl2] (1) with UV light in CH2Cl2-MeCN and tetrahydrofuran (thf)-H2O afforded [LOEtRuCl 2(MeCN)] (5) and the chloro-bridged dimer [LOEtRuCl] 2(μ-Cl)2 (6), respectively. The photolysis of complex [2][OTf]2 in MeCN gave [LOEtRu(dtbpy)(MeCN)][OTf] 2 (7). Refluxing complex 5 with RNH2 in thf gave [L OEtRuCl2(NH2R)] (R = tBu (8), p-tol (9), Ph (10)). The oxidation of complex 6 with PhICl2 gave [L OEtRuCl3] (11), whereas the reduction of complex 6 with Zn and NH4PF6 in MeCN yielded [LOEtRu(MeCN) 3][PF6] (12). The reaction of 3·[BF 4]2 with benzylamine afforded the μ-dinitrogen complex [{LOEtRu(bpy)}2(μ-N2)][BF4] 2 (13) that was oxidized by [Cp2Fe]PF6 to a mixed valence RuII,III species. The formal potentials of the RuL OEt complexes have been determined by cyclic voltammetry. The structures of complexes 5,6,10,11 and 13 have been established by X-ray crystallography.",

author = "Ip, {Ho Fai} and Yi, {Xiao Yi} and WONG, {Wai Yeung} and Williams, {Ian D.} and Leung, {Wa Hung}",

year = "2011",

month = nov,

day = "7",

doi = "10.1039/c1dt10306g",

language = "English",

volume = "40",

pages = "11043--11050",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "41",

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TY - JOUR

T1 - Synthesis, structures and reactivity of ruthenium nitrosyl complexes containing Kläui's oxygen tripodal ligand

AU - Ip, Ho Fai

AU - Yi, Xiao Yi

AU - WONG, Wai Yeung

AU - Williams, Ian D.

AU - Leung, Wa Hung

PY - 2011/11/7

Y1 - 2011/11/7

N2 - Ruthenium nitrosyl complexes containing the Kläui's oxgyen tripodal ligand LOEt- ([CpCo{P(O)(OEt)2} 3]- where Cp = η5-C5H 5) were synthesized and their photolysis studied. The treatment of [Ru(NN)(NO)Cl3] with [AgLOEt] and Ag(OTf) afforded [L OEtRu(NN)(NO)][OTf]2 where NN = 4,4′-di-tert-butyl- 2,2′-bipyridyl (dtbpy) (2·[OTf]2), 2,2′-bipyridyl (bpy) (3·[OTf]2), N,N,N′N′- tetramethylethylenediamine (4·[OTf]2). Anion metathesis of 3·[OTf]2 with HPF6 and HBF4 gave 3·[PF6]2 and 3·[BF4]2, respectively. Similarly, the PF6- salt 4·[PF 6]2 was prepared by the reaction of 4·[OTf] 2 with HPF6. The irradiation of [LOEtRu(NO) Cl2] (1) with UV light in CH2Cl2-MeCN and tetrahydrofuran (thf)-H2O afforded [LOEtRuCl 2(MeCN)] (5) and the chloro-bridged dimer [LOEtRuCl] 2(μ-Cl)2 (6), respectively. The photolysis of complex [2][OTf]2 in MeCN gave [LOEtRu(dtbpy)(MeCN)][OTf] 2 (7). Refluxing complex 5 with RNH2 in thf gave [L OEtRuCl2(NH2R)] (R = tBu (8), p-tol (9), Ph (10)). The oxidation of complex 6 with PhICl2 gave [L OEtRuCl3] (11), whereas the reduction of complex 6 with Zn and NH4PF6 in MeCN yielded [LOEtRu(MeCN) 3][PF6] (12). The reaction of 3·[BF 4]2 with benzylamine afforded the μ-dinitrogen complex [{LOEtRu(bpy)}2(μ-N2)][BF4] 2 (13) that was oxidized by [Cp2Fe]PF6 to a mixed valence RuII,III species. The formal potentials of the RuL OEt complexes have been determined by cyclic voltammetry. The structures of complexes 5,6,10,11 and 13 have been established by X-ray crystallography.

AB - Ruthenium nitrosyl complexes containing the Kläui's oxgyen tripodal ligand LOEt- ([CpCo{P(O)(OEt)2} 3]- where Cp = η5-C5H 5) were synthesized and their photolysis studied. The treatment of [Ru(NN)(NO)Cl3] with [AgLOEt] and Ag(OTf) afforded [L OEtRu(NN)(NO)][OTf]2 where NN = 4,4′-di-tert-butyl- 2,2′-bipyridyl (dtbpy) (2·[OTf]2), 2,2′-bipyridyl (bpy) (3·[OTf]2), N,N,N′N′- tetramethylethylenediamine (4·[OTf]2). Anion metathesis of 3·[OTf]2 with HPF6 and HBF4 gave 3·[PF6]2 and 3·[BF4]2, respectively. Similarly, the PF6- salt 4·[PF 6]2 was prepared by the reaction of 4·[OTf] 2 with HPF6. The irradiation of [LOEtRu(NO) Cl2] (1) with UV light in CH2Cl2-MeCN and tetrahydrofuran (thf)-H2O afforded [LOEtRuCl 2(MeCN)] (5) and the chloro-bridged dimer [LOEtRuCl] 2(μ-Cl)2 (6), respectively. The photolysis of complex [2][OTf]2 in MeCN gave [LOEtRu(dtbpy)(MeCN)][OTf] 2 (7). Refluxing complex 5 with RNH2 in thf gave [L OEtRuCl2(NH2R)] (R = tBu (8), p-tol (9), Ph (10)). The oxidation of complex 6 with PhICl2 gave [L OEtRuCl3] (11), whereas the reduction of complex 6 with Zn and NH4PF6 in MeCN yielded [LOEtRu(MeCN) 3][PF6] (12). The reaction of 3·[BF 4]2 with benzylamine afforded the μ-dinitrogen complex [{LOEtRu(bpy)}2(μ-N2)][BF4] 2 (13) that was oxidized by [Cp2Fe]PF6 to a mixed valence RuII,III species. The formal potentials of the RuL OEt complexes have been determined by cyclic voltammetry. The structures of complexes 5,6,10,11 and 13 have been established by X-ray crystallography.

UR - http://www.scopus.com/inward/record.url?scp=80053995809&partnerID=8YFLogxK

U2 - 10.1039/c1dt10306g

DO - 10.1039/c1dt10306g

M3 - Journal article

AN - SCOPUS:80053995809

SN - 1477-9226

VL - 40

SP - 11043

EP - 11050

JO - Dalton Transactions

JF - Dalton Transactions

IS - 41

ER -

Synthesis, structures and reactivity of ruthenium nitrosyl complexes containing Kläui's oxygen tripodal ligand

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