NDLI: Organometallic–Inorganic Conjugated Unsymmetrical Schiff-Base Hybrids. Synthesis, Characterization, Electrochemistry and X-ray Crystal Structures of Functionalized Trinuclear Iron–Nickel

Content Provider	Springer Nature Link
Author	Trujillo, Alexander Sinbandhit, Sourisak Toupet, Loïc Carrillo, David Manzur, Carolina Hamon, Jean René
Copyright Year	2007
Abstract	The synthesis of neutral dinuclear iron–nickel unsymmetrical Schiff base complexes 3 and 4 was achieved via a template reaction involving equimolar amounts of alkyl or aryl “half-unit” precursors, respectively, Fc–C(O)CH=C(CH$_{3}$)N(H)R (1: R = CH$_{2}$CH$_{2}$NH$_{2}$; 2: R = o-C$_{6}$H$_{4}$NH$_{2}$; Fc = CpFe(η$^{5}$-C$_{5}$H$_{4}$); Cp = η$^{5}$-C$_{5}$H$_{5}$), 5-bromosalicylaldehyde and nickel(II) acetate tetrahydrate in a refluxing CH$_{2}$Cl$_{2}$/MeOH (1:1) mixture. The ionic trinuclear unsymmetrical complex 5 was prepared by reacting its dinuclear precursor 3 with the arenophile source, [CpRu(NCCH$_{3}$)$_{3}$]PF$_{6}$ (Cp = η$^{5}$-C$_{5}$(CH$_{3}$)$_{5}$), in refluxing CH$_{2}$Cl$_{2}$ for 2 h, whereas the trinuclear species 6 was formed upon regioselective π-complexation of the 5-bromosalicylidene ring of 4 by [Cp*Ru]$^{+}$ at room temperature overnight. All the new compounds were adequately characterized by analytical and spectroscopic techniques and, in addition, the crystal and molecular structures of the “half-unit” 1, the binuclear complex 4 and its hemisolvate adduct 4 · 0.5CH$_{3}$OH, the trinuclear Schiff base compound 5 · 2(CH$_{3}$)$_{2}$CO, and the mixed sandwich metalloligand 7 have been determined by X-ray crystallography. Both organometallic–inorganic hybrids 5 and 6 contain the neutral electron-releasing ferrocenyl group, and the cationic electron-withdrawing ruthenium mixed sandwich, linked through the unsymmetrical tetradentate Schiff base complex {Ni(ONNO)}. UV–vis, $^{1}$H and $^{13}$C NMR as well as electrochemical data clearly indicate a mutual donor–acceptor electronic influence between the organometallic termini. Furthermore, X-ray crystal structure analysis of 5 · 2(CH$_{3}$)$_{2}$CO reveals the partial delocalization of bonding electron density throughout the dinucleating nickel Schiff base ligand.
Starting Page	81
Ending Page	99
Page Count	19
File Format	PDF
ISSN	15741443
Journal	Journal of Inorganic and Organometallic Polymers and Materials
Volume Number	18
Issue Number	1
e-ISSN	15741451
Language	English
Publisher	Springer US
Publisher Date	2007-11-29
Publisher Place	Boston
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Ferrocenyl ketoamine Unsymmetrical Schiff base complexes Push-pull complexes Trinuclear iron–nickel–ruthenium complexes Crystal structure Polymer Sciences Organic Chemistry Inorganic Chemistry
Content Type	Text
Resource Type	Article
Subject	Materials Chemistry Polymers and Plastics

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