کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1324727 1499921 2012 10 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Synthesis, molecular structure and electrochemistry of gold(I) complexes with 1-(diphenylphosphino)-1′-[(diphenylphosphino)methyl]ferrocene
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی معدنی
پیش نمایش صفحه اول مقاله
Synthesis, molecular structure and electrochemistry of gold(I) complexes with 1-(diphenylphosphino)-1′-[(diphenylphosphino)methyl]ferrocene
چکیده انگلیسی

Depending on the reaction stoichiometry, 1-(diphenylphosphino)-1′-[(diphenylphosphino)methyl]-ferrocene (1) reacts with [AuCl(tht)] (tht = tetrahydrothiophene) to afford an insoluble polymer formulated as [AuCl(1)]n (2) or ligand-bridged digold(I) complex, [(μ-1)(AuCl)2] (3). The latter compound readily undergoes metathesis reactions with anionic reagents such as in situ generated acetylides, thiocyanate or N,N-diethyldithiocarbamate to give the corresponding digold(I) complexes [(μ-1)(AuY)2], where Y is CCPh (4), CCFc (5; Fc = ferrocenyl), SCN (6), and Et2NCS2 (7). Similar reaction of 3 with a dithiolate formed from propane-1,3-dithiol and sodium methoxide affords a macrocyclic bis-chelate [(μ-1)(AuSCH2CH2CH2SAu)] (8). Compounds 2–8 have been characterized by spectroscopic methods (multinuclear NMR, ESI, MS, UV–vis and IR) and by elemental analysis, and the molecular structures of 3·½C2H4Cl2, 4·2CHCl3, 7·2CHCl3, and 8 have been determined by single-crystal X-ray diffraction analysis. Cyclic voltammetric study revealed that ligand 1 undergoes a one-electron oxidation at the ferrocene unit, which is associated with some chemical complications resulting presumably from the presence of the lone electron pair at phosphorus. After coordination to Au(I)L fragments bearing simple auxiliary ligands (e.g., in 3, 4, and 6), the FeII/FeIII redox process becomes reversible and appears shifted to more positive potentials owing to an electron density transfer from the diphosphine ligand to the coordinated metal centers. For compounds 5 and 7, this redox change is accompanied by additional waves attributable to oxidation of ferrocenyl groups in the terminal ferrocenylethynyl groups and to redox changes occurring at the Au-bound carbamate ligands, respectively.

Stable diphosphine-bridged digold(I) complex [(Ph2PfcCH2PPh2)(AuCl)2] (fc = ferrocene-1,1′-diyl), resulting by the reaction of Ph2PfcCH2PPh2 with [AuCl(tht)] (tht = tetrahydrothiophene; see Figure), represents a convenient entry to other non-symmetric Au2Fe trimetallic complexes via metathesis-like reactions with various anionic reagents.Figure optionsDownload as PowerPoint slideHighlights
► Gold(I) complexes with a non-symmetric metallophosphine, [Fe(η5-C5H4PPh2)(η5-C5H4CH2PPh2)].
► Preparation of Au2Fe trimetallic complexes via salt metathesis.
► Electrochemical response changes upon introduction of redox-active terminal ligands.

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Organometallic Chemistry - Volume 716, 1 October 2012, Pages 110–119
نویسندگان
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