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Permanent URL to this publication: http://dx.doi.org/10.5167/uzh-32316

Fritz, T; Schmalle, H W; Blacque, O; Venkatesan, K; Berke, H (2009). Synthesis and characterization of mononuclear and dinuclear manganese bis-acetylide complexes. Zeitschrift für Anorganische und Allgemeine Chemie, 635(9-10):1391-1401.

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Abstract

The symmetric d5 trans-bis-alkynyl complexes {Mn[(Me)2P(CH2)nP(Me)2]2(CCC6H4R)2} (n = 2, R = -CCTIPS (2a); n = 3, R = -CCTIPS (2b); n = 2, R = F (4); n = 3; -CCTIPS) were prepared by the reaction of [Mn(dmpe)2Br2] with two equivalents of the corresponding acetylide LiCCC6H4R (R = F, -CCTIPS). The reaction of compounds 2a, 2b and 4 with [Cp2Fe][PF6] yielded the corresponding d4 complexes {Mn[(Me)2P(CH2)nP(Me)2]2(CCC6H4R)2}[PF6] (n = 2, R = -CCTIPS, [2a]+; n = 3, R = -CCTIPS, [2b]+;n = 2, R = F, [4]+; n = 3; -CCTIPS). The unsymmetrically substituted trans-iodo-alkynyl complex [IMn(dmpe)2(CCC6H4-CCTIPS)] (5) was obtained by treating MeCpMn(dmpe)I with one equivalent of H-CCC6H4-CCTIPS in the presenceof dmpe. Deprotection of the TIPS group with TBAF gavecomplex [IMn(dmpe)2(CCC6H4CCH)] (6) in 94 % yield. The neutral dinuclear complexes MnII/MnII compounds {[Mn((Me)2P(CH2CH2)P(Me)2)2(CCC6H4R)]2(-C4)} (R = H, Me, n-pentyl, F) were prepared by the direct reaction of {[Mn((Me)2P(CH2CH2)P(Me)2)2I]2(-C4)} with the corresponding LiCCC6H4R (R = H, n-pentyl, F). These MnII/MnII 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.

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Institute of Inorganic Chemistry
DDC:540 Chemistry
Uncontrolled Keywords:Mixed-valent compounds; Molecular devices; Molecular wires; Nanotechnology; Single-electron devices
Language:English
Date:2009
Deposited On:03 Mar 2010 13:53
Last Modified:28 Nov 2013 00:51
Publisher:Wiley-Blackwell
ISSN:0044-2313
Funders:Swiss National Science Foundation (SNSF), University of Zurich
Publisher DOI:10.1002/zaac.200801423
Citations:Web of Science®
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