Synthesis and characterization of mononuclear and dinuclear manganese bis-acetylide complexes

Thorsten Fritz, Helmut W. Schmalle, Olivier Blacque, Koushik Venkatesan, Heinz Berke*

*Corresponding author for this work

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Abstract

The symmetric d5 trans-bis-alkynyl complexes {Mn[(Me) 2P(CH2)nP(Me)2]2(C= CC6H4R)2} (n = 2, R = -C=CTIPS (2a); n = 3, R = -C=CTIPS (2b); n = 2, R = F (4); n = 3; -C=CTIPS) were prepared by the reaction of [Mn(dmpe)2Br2] with two equivalents of the corresponding acetylide LiC=CC6H4R (R = F, -C=CTIPS). The reaction of compounds 2a, 2b and 4 with [Cp2Fe][PF6] yielded the corresponding d4 complexes {Mn[(Me)2P(CH 2)nP(Me)2]2(C=CC6H 4R)2}[PF6] (n = 2, R = -C=CTIPS, [2a] +; n = 3, R = -C=CTIPS, [2b]+; n = 2, R = F, [4] +; n = 3; -C=CTIPS). The unsymmetrically substituted trans-iodo-alkynyl complex [IMn(dmpe)2(C= CC6H 4C=CTIPS)] (5) was obtained by treating MeCpMn(dmpe)I with one equivalent of H-C=CC6H4-C=CTIPS in the presence of dmpe. Deprotection of the TIPS group with TBAF gave complex [IMn(dmpe) 2(C=CC6H4C=CH)] (6) in 94% yield. The neutral dinuclear complexes MnII/MnII compounds {[Mn((Me) 2P(CH2CH2)P(Me)2) 2(C=CC6H4R)]2(μ-C4)} (R = H, Me, n-pentyl, F) were prepared by the direct reaction of {[Mn((Me) 2P(CH2CH2)P(Me)2)2I] 2(μ-C4)} with the corresponding LiC=CC 6H4R (R = H, n-pentyl, F). These MnII/Mn II dinuclear compounds were further oxidized to the mixed-valent complexes and the dicationic complexes using [Cp2Fe][PF6]. All complexes have been characterized by NMR, IR, and Raman spectroscopy. X-ray diffraction studies were carried out on complexes 1c, 2a, 4, [4]+, and 6.

Original languageEnglish
Pages (from-to)1391-1401
Number of pages11
JournalZeitschrift fur Anorganische und Allgemeine Chemie
Volume635
Issue number9-10
DOIs
Publication statusPublished - Jul 2009
Externally publishedYes

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Keywords

  • Mixed-valent compounds
  • Molecular devices
  • Molecular wires
  • Nanotechnology
  • Single-electron devices

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