Reactions of [RuCl2(NO)(terpy)]+ (terpy = 2,2′ : 6′,2″-terpyridine) with mono anions such as NO2–, Br– and N3–, and structural studies on terpyridineruthenium having a nitrosyl ligand

Hirano, Tôru; Ueda, Koji; Mukaida, Masao; Nagao, Hidemi; Oi, Takao

doi:10.1039/b101546j

Cited by 40 publications

(41 citation statements)

References 25 publications

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“…RuCl 2 (RaaiR¢) 2 (4)(5)(6). In nitroso derivatives, [Ru(NO 2 )(NO)(OMeaaiR¢) 2 ](ClO 4 ) 2 (10b-12b) the intense absorption bands are further shifted to shorter wavelength, 400-420 nm along with a weak band at 600-620 nm.…”

Section: Synthesis and Formulationmentioning

confidence: 95%

“…This is certainly due to the stretching mode of m(NO) of the coordinated nitrosyl group [3,4,11]. Nitric oxide formally acts as a cationic donor (NO + ) and binds both in the linear and bent NAO fashion.…”

Section: Synthesis and Formulationmentioning

confidence: 98%

“…The mononitrosyls, [Ru(NO 2 )(NO)(OMeaaiR¢) 2 ] (ClO 4 ) 2 exhibit similar pattern of signals in the aromatic portion and the spectra have been shifted to higher field by 0.03-0.15 ppm from those of respective dinitro derivatives. It may presumably be due to better dp(Ru) fi p*(NO) charge transfer [3,4,11] which increases the hardness of Ru(II) leading to strong r-interaction with the chelator, OMeaaiR¢. The transformation, Ru(NO 2 ) 2 (OMeaaiR¢) 2 fi [Ru(NO 2 )(NO) (OMeaaiR¢) 2 ] 2+ reduces the overall symmetry of the product (C 2 fi C 1 ) and is supported through appearance of two Ar-Me signals at 2.4 and 2.2 ppm in (10b-12b).…”

Section: Synthesis and Formulationmentioning

confidence: 99%

“…Diaquo complexes ctc-[Ru(OH 2 ) 2 (RaaiR¢) 2 ](ClO 4 ) 2 , prepared by Ag + -assisted aquation of ctc-RuCl 2 (RaaiR¢) 2 (4)(5)(6), were reacted with NaNO 2 (excess amount >3 mol) under stirring at 343-353 K in aqueous alcohol to give Ru(NO 2 ) 2 (RaaiR¢) 2 (7)(8)(9) in good yield (65-85%). The synthetic routes are shown in Scheme 1.…”

Section: Synthesis and Formulationmentioning

confidence: 99%

“…The search for a suitable precursor to synthesize NO-complexes is a challenging domain and nitrite compounds are found to be useful in this context [6]. Recently, we have developed the arylazoimidazole chemistry of ruthenium and have synthesised dichloro compounds RuCl 2 (RaaiR¢) 2 (4)(5)(6) and diaquo species [Ru(OH 2 ) 2 (RaaiR¢) 2 ] 2+ [RaaiR¢¼ p-RAC 6 H 4 AN@NAC 3 H 2 ANNA1AR¢, (1)(2)(3), R = H, OMe, NO 2 and R¢ = Me, CH 2 CH 3 , CH 2 Ph abbreviated as N,N¢-chelator where N(imidazole) and N(azo) represent N and N¢, respectively]. Syntheses of hetero-tris-chelates, [Ru(bpy) n (RaaiR¢) 3)n ] (ClO 4 ) 2 [bpy = 2,2¢-bipyridine; n = 1, n=2) from the solvento complexes [Ru(OH 2 ) 2 (bpy) 2 ] 2+ /[Ru(OH 2 ) 2 (Raai R¢) 2 ] 2+ containing labile reaction centres are reported from my laboratory [8].…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Spectra and Electrochemistry of Dinitro-bis-{1-alkyl-2-(arylazo) imidazole} Ruthenium(II). Nitro-nitroso Derivatives and Reactivity of the Electrophilic {Ru-NO}6System

Byabartta

2005

Transition Met Chem

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Ag + assisted aquation of blue cis-trans-cis-RuCl 2 (RaaiR¢) 2 (4-6) leads to the synthesis of solvento species, blueviolet cis-trans-cis-[Ru(OH 2 ) 2 (RaaiR¢) 2 ](ClO 4 ) 2 [Raai R¢=p-RAC 6 H 4 AN@NAC 3 H 2 ANNA1AR¢, (1-3), abbreviated as N, N¢-chelator, where N(imidazole) and N(azo) represent N and N¢, respectively; R = H (a), OMe (b), NO 2 (c) and R¢ = Me (1/4/7/10), CH 2 CH 3 (2/5/8/11), CH 2 Ph (3/6/9/12)] that have been reacted with NO 2 ) in warm EtOH resulting in violet dinitro complexes of the type, Ru(NO 2 ) 2 (RaaiR¢) 2 (7-9). The nitrite complexes are useful synthons of electrophilic nitrosyls, and on triturating the compounds, (7b-9b) with conc. HClO 4 nitronitrosyl derivatives, [Ru(NO 2 )(NO)(OMeaaiR¢) 2 ](ClO 4 ) 2 (10b-12b) are isolated. The solution structure and stereoretentive transformation in each step have been established from 1 H n.m.r. results. All the complexes exhibit strong MLCT transitions in the visible region. They are redox active and display one metal-centred oxidation and successive ligand-based reductions. The redox potentials of Ru(III)/Ru(II) (E 1/2 M ) of (10b-12b) are anodically shifted by $0.2 V as compared to those of dinitro precursors, (7b-9b). The m(NO) >1900 cm )1 strongly suggests the presence of linear RuANO bonding. The electrophilic behaviour of metal bound nitrosyl has been proved in one case (12b) by reacting with a bicyclic ketone, camphor, containing an active methylene group and an arylhydrazone with an active methine group, and the heteroleptic tris chelates thus formed have been characterised.

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Section: Synthesis and Formulationmentioning

confidence: 95%

Section: Synthesis and Formulationmentioning

confidence: 98%

Section: Synthesis and Formulationmentioning

confidence: 99%

Section: Synthesis and Formulationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis, Spectra and Electrochemistry of Dinitro-bis-{1-alkyl-2-(arylazo) imidazole} Ruthenium(II). Nitro-nitroso Derivatives and Reactivity of the Electrophilic {Ru-NO}6System

Byabartta

2005

Transition Met Chem

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Photocrystallographic, Spectroscopic, and Calorimetric Analysis of Light‐Induced Linkage NO Isomers in [RuNO(NO₂)₂(pyridine)₂OH]

et al. 2015

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Reaction of [RuNO(NO₂)₄OH]^2– with Sulfamic Acid as a Pathway to Mixed Nitro Pyridine Ruthenium Nitrosyl Complexes

et al. 2016

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The transformations of [RuNO(NO2)4OH]2– during sequential treatment with sulfamic acid and pyridine have been investigated by 15N NMR spectroscopy. Depending on the initial molar ratio of Ru/NH2SO3H, the first stage of the reaction at room temperature in an aqueous solution proceeded with stoichiometric removal of one or two NO2 ligands and may be accompanied by ligand redistribution and partial isomerization NO2/ONO. Further treatment with pyridine resulted in the replacement of labile ligands (H2O, SO4) and the formation of mixed nitro pyridine complexes of ruthenium nitrosyl. Mixed nitrito‐N‐nitrito‐O complexes PyH[RuNO(NO2)2(ONO)Py(OH)] and OC‐6‐34‐[RuNO(NO2)(ONO)Py2OH] as well as the dimeric ruthenium complex with µ‐bridging oxo groups NH4[Ru(NO)Py3(µ‐O)]2(PF6)3 were separated as solids and structurally characterized. The photochemical isomerization (445 nm, 9 K) of Ru–NO with the formation of metastable isonitrosyl complexes was found for all the prepared compounds; the population of the metastable state did not exceed 20 %.

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Reactions of [RuCl2(NO)(terpy)]+ (terpy = 2,2′ : 6′,2″-terpyridine) with mono anions such as NO2–, Br– and N3–, and structural studies on terpyridineruthenium having a nitrosyl ligand

Cited by 40 publications

References 25 publications

Synthesis, Spectra and Electrochemistry of Dinitro-bis-{1-alkyl-2-(arylazo) imidazole} Ruthenium(II). Nitro-nitroso Derivatives and Reactivity of the Electrophilic {Ru-NO}6System

Synthesis, Spectra and Electrochemistry of Dinitro-bis-{1-alkyl-2-(arylazo) imidazole} Ruthenium(II). Nitro-nitroso Derivatives and Reactivity of the Electrophilic {Ru-NO}6System

Photocrystallographic, Spectroscopic, and Calorimetric Analysis of Light‐Induced Linkage NO Isomers in [RuNO(NO₂)₂(pyridine)₂OH]

Reaction of [RuNO(NO₂)₄OH]^2– with Sulfamic Acid as a Pathway to Mixed Nitro Pyridine Ruthenium Nitrosyl Complexes

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Reactions of [RuCl2(NO)(terpy)]+ (terpy = 2,2′ : 6′,2″-terpyridine) with mono anions such as NO2–, Br– and N3–, and structural studies on terpyridineruthenium having a nitrosyl ligand

Cited by 40 publications

References 25 publications

Synthesis, Spectra and Electrochemistry of Dinitro-bis-{1-alkyl-2-(arylazo) imidazole} Ruthenium(II). Nitro-nitroso Derivatives and Reactivity of the Electrophilic {Ru-NO}6System

Synthesis, Spectra and Electrochemistry of Dinitro-bis-{1-alkyl-2-(arylazo) imidazole} Ruthenium(II). Nitro-nitroso Derivatives and Reactivity of the Electrophilic {Ru-NO}6System

Photocrystallographic, Spectroscopic, and Calorimetric Analysis of Light‐Induced Linkage NO Isomers in [RuNO(NO2)2­(pyridine)2OH]

Reaction of [RuNO(NO2)4OH]2– with Sulfamic Acid as a Pathway to Mixed Nitro Pyridine Ruthenium Nitrosyl Complexes

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Product

Resources

About

Photocrystallographic, Spectroscopic, and Calorimetric Analysis of Light‐Induced Linkage NO Isomers in [RuNO(NO₂)₂(pyridine)₂OH]

Reaction of [RuNO(NO₂)₄OH]^2– with Sulfamic Acid as a Pathway to Mixed Nitro Pyridine Ruthenium Nitrosyl Complexes