Facile access to redox-active C2-bridged complexes with half-sandwich manganese end groups

Chemistry : a European Journal
S KheradmandanHeinz Berke

Abstract

The dinuclear mixed-valent complex [(MeC5H4)(dmpe)MnC(2)Mn(dmpe)(C5H4Me)](+)[(eta2-MeC5H4)3Mn](-)[1](+)[2]- (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 [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.

Citations

Mar 7, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Koushik VenkatesanHeinz Berke
Oct 28, 2016·Chemistry : a European Journal·Kentaro MishibaMunetaka Akita
Apr 23, 2005·Chemical Communications : Chem Comm·Christoph ElschenbroichKlaus Harms
Nov 21, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Michael I BruceAllan H White
Aug 18, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Michael I BruceAllan H White
Jul 26, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Kiyotaka OnitsukaShigetoshi Takahashi
Apr 4, 2019·Angewandte Chemie·Benjamin J Frogley, Anthony F Hill
Mar 12, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Karine Costuas, Stéphane Rigaut
Aug 30, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Andie R DelaneyAnthony F Hill
Apr 21, 2010·Chemical Reviews·Paulina Aguirre-Etcheverry, Dermot O'Hare
Aug 3, 2013·Inorganic Chemistry·Daniel E HainesMichael D Hopkins
Nov 10, 2011·Journal of the American Chemical Society·Wesley A HoffertMatthew P Shores

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