Kheradmandan, S; Venkatesan, K; Blacque, Olivier; Schmalle, H W; Berke, Heinz (2004). Facile access to redox-active C2-bridged complexes with half-sandwich manganese end groups. Chemistry - A European Journal, 10(19):4872-4885.
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The dinuclear mixed-valent complex [(MeC5H4)(dmpe)MnC(2)Mn(dmpe)(C5H4Me)](+)[(eta2-MeC5H4)3Mn](-)(+)- (dmpe=1,2-bis(dimethylphosphanyl)ethane) was prepared by the reaction of [Mn(MeC5H4)2] with dmpe and Me(3)SnC[triple chemical bond]CSnMe3. The reactions of (+)- with K[PF6] and Na[BPh4] yielded the corresponding anion metathesis products [(MeC5H4)(dmpe)MnC2Mn(dmpe)(C5H4Me)][PF6] ([PF6]) and [(MeC5H4)(dmpe)MnC2Mn(dmpe)(C5H4Me)][BPh4] ([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 ([PF6]2) was obtained by oxidizing the mixed-valent complex [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 , [PF6], [BPh4], and [PF6]2.
|Item Type:||Journal Article, refereed|
|Communities & Collections:||07 Faculty of Science > Department of Chemistry|
|Date:||4 October 2004|
|Deposited On:||11 Feb 2008 12:25|
|Last Modified:||27 Nov 2013 17:14|
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