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

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

doi:10.1002/zaac.200801423

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

Research output: Contribution to journal › Article › peer-review

8 Citations (Scopus)

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 Mn^II/Mn^II 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 Mn^II/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 language	English
Pages (from-to)	1391-1401
Number of pages	11
Journal	Zeitschrift fur Anorganische und Allgemeine Chemie
Volume	635
Issue number	9-10
DOIs	https://doi.org/10.1002/zaac.200801423
Publication status	Published - Jul 2009
Externally published	Yes

Keywords

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

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10.1002/zaac.200801423

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@article{4afa2e4b72b14295a08e924ccc512f44,

title = "Synthesis and characterization of mononuclear and dinuclear manganese bis-acetylide complexes",

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.",

keywords = "Mixed-valent compounds, Molecular devices, Molecular wires, Nanotechnology, Single-electron devices",

author = "Thorsten Fritz and Schmalle, \{Helmut W.\} and Olivier Blacque and Koushik Venkatesan and Heinz Berke",

year = "2009",

month = jul,

doi = "10.1002/zaac.200801423",

language = "English",

volume = "635",

pages = "1391--1401",

journal = "Zeitschrift fur Anorganische und Allgemeine Chemie",

issn = "0044-2313",

publisher = "Wiley-VCH, Wiley",

number = "9-10",

}

TY - JOUR

T1 - Synthesis and characterization of mononuclear and dinuclear manganese bis-acetylide complexes

AU - Fritz, Thorsten

AU - Schmalle, Helmut W.

AU - Blacque, Olivier

AU - Venkatesan, Koushik

AU - Berke, Heinz

PY - 2009/7

Y1 - 2009/7

N2 - 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.

AB - 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.

KW - Mixed-valent compounds

KW - Molecular devices

KW - Molecular wires

KW - Nanotechnology

KW - Single-electron devices

UR - https://www.scopus.com/pages/publications/69249154558

U2 - 10.1002/zaac.200801423

DO - 10.1002/zaac.200801423

M3 - Article

AN - SCOPUS:69249154558

SN - 0044-2313

VL - 635

SP - 1391

EP - 1401

JO - Zeitschrift fur Anorganische und Allgemeine Chemie

JF - Zeitschrift fur Anorganische und Allgemeine Chemie

IS - 9-10

ER -

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

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