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

Sohrab Kheradmandan, Koushik Venkatesan, Olivier Blacque, Helmut W. Schmalle, Heinz Berke*

*Corresponding author for this work

Research output: Contribution to journalArticle

47 Citations (Scopus)

Abstract

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(MeC 5H4)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)Mn-C 2Mn(dmpe)(C5H4Me)][PF6] ([1][PF 6]) 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)MnC 2Mn(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)(C 5H4Me)][PF6]2 ([1][PF 6]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.

Original languageEnglish
Pages (from-to)4872-4885
Number of pages14
JournalChemistry - A European Journal
Volume10
Issue number19
DOIs
Publication statusPublished - 4 Oct 2004
Externally publishedYes

Keywords

  • Alkyne ligands
  • Density functional calculations
  • Half-sandwich complexes
  • Manganese
  • Mixed-valent compounds

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