Facile Access to Redox‐Active C2‐Bridged Complexes with Half‐Sandwich Manganese End Groups

Autor: Kheradmandan, Sohrab, Venkatesan, Koushik, Blacque, Olivier, Schmalle, Helmut W., Berke, Heinz
Zdroj: Chemistry - A European Journal; October 2004, Vol. 10 Issue: 19 p4872-4885, 14p
Abstrakt: The dinuclear mixed‐valent complex [(MeC5H4)(dmpe)MnC2Mn(dmpe)(C5H4Me)]+[(η2‐MeC5H4)3Mn]−[1]+[2]−(dmpe=1,2‐bis(dimethylphosphanyl)ethane) was prepared by the reaction of [Mn(MeC5H4)2] with dmpe and Me3SnCCSnMe3. The reactions of [1]+[2]−with K[PF6] and Na[BPh4] yielded the corresponding anion metathesis products [(MeC5H4)(dmpe)MnC2Mn(dmpe)(C5H4Me)][PF6] ([1][PF6]) and [(MeC5H4)(dmpe)MnC2Mn(dmpe)(C5H4Me)][BPh4] ([1][BPh4]). These mixed‐valent species can be reduced to the neutral form by reaction with Na/Hg. The obtained complex [(MeC5H4)(dmpe)MnC2Mn(dmpe)(C5H4Me)] (1) displays a triplet/singlet spin equilibrium in solution and in the solid state, which was additionally studied by DFT calculations. The diamagnetic dicationic species [(MeC5H4)(dmpe)MnC2Mn(dmpe)(C5H4Me)][PF6]2([1][PF6]2) was obtained by oxidizing the mixed‐valent complex [1][PF6] with one equivalent of [Fe(C5H5)2][PF6]. Both redox processes are fully reversible. The dinuclear compounds were characterized by NMR, IR, UV‐visible, and Raman spectroscopy, cyclic voltammetry, and magnetic susceptibility measurements. X‐ray diffraction studies were performed on [1][2], [1][PF6], [1][BPh4], and [1][PF6]2.
Databáze: Supplemental Index
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