کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1312574 975467 2010 11 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Solvent and electrolyte effects in enhancing the identification of intramolecular electronic communication in a multi redox-active diruthenium tetraferrocenoate complex, a triple-sandwiched dicadmium phthalocyanine and a ruthenocene-containing β-diketone
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی معدنی
پیش نمایش صفحه اول مقاله
Solvent and electrolyte effects in enhancing the identification of intramolecular electronic communication in a multi redox-active diruthenium tetraferrocenoate complex, a triple-sandwiched dicadmium phthalocyanine and a ruthenocene-containing β-diketone
چکیده انگلیسی

Enhanced electrochemical resolution of anodic processes is possible in the presence of [N(nBu)4][B(C6F5)4], 1, as supporting electrolyte over that obtained in the presence of [N(nBu)4][PF6]. By changing the anion of the supporting electrolyte to a salt having [B(C6F5)4]−, anions, electrochemical processes of especially cationic analytes can benefit. Thus, the redox chemistry of 0.5 mmol dm−3 solutions of [Ru2(μ-FcCOO)4·(CH3CH2OH)2][PF6], 2, Fc = ferrocenyl, in CH2Cl2/[N(nBu)4][B(C6F5)4] were found to involve four well-resolved ferrocenyl-based electrochemical reversible redox processes as well as reduction of RuIII–RuII. At 1.0 mmol dm−3 concentrations of 2, or in the presence of [N(nBu)4][PF6], the four ferrocenyl processes coalesced into only two waves as a result of (Fc+)⋯(PF6-) ion paring. Seventeen of the possible 18 one-electron transfer processes of the biscadmium trisphthalocyaninato complex [Cd2{Pc(C6H13)8}3], 3, could be observed in THF/[N(nBu)4][B(C6F5)4], but the electrochemical window of CH2Cl2/[N(nBu)4][B(C6F5)4] only allowed detection of 15 of these processes. Although reduction processes were unaffected, THF solvation leading to species such as (3n+)(THF)x with 1 ⩽ n ⩽ 4 and x ⩾ 1 as well as ion pair formation of the type (3n+)⋯(PF6-) prevented good resolution of oxidation processes. The CH2Cl2/[N(nBu)4][B(C6F5)4] system also allowed detection of reversible one-electron transfer ferrocenyl (Fc/Fc+) and ruthenocenyl-based (Rc/Rc+) processes for both enol and keto isomers of the β-diketone FcCOCH2CORc, 4, Rc = ruthenocenyl. In CH3CN/[N(nBu)4][PF6], the ruthenocenyl moiety was oxidised to a RuIV species.

Less ion pair formation between oxidised intermediates and the electrolyte [N(nBu)4][B(C6F5)4] as compared with PF6- salts allowed electrochemical detection of up to 17 well-resolved one-electron transfer processes for the phthalocyanine [Cd2{Pc(C6H13)8}3], four for the β-diketone FcCOCH2CORc and five for [Ru2(μ-FcCOO)4·(ethanol)2][PF6]; THF as solvent enhanced peak resolution of reduced (negatively charged) species, while CH3CN complicated electrochemical interpretations due to coordination reactions.Figure optionsDownload as PowerPoint slide

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Inorganica Chimica Acta - Volume 363, Issue 10, 20 June 2010, Pages 2222–2232
نویسندگان
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