Hydrocarbon-soluble, hexaanionic fulleride complexes of magnesium

Samuel Lawrence; C. André Ohlin; David B. Cordes; Alexandra M. Z. Slawin; Andreas Stasch

doi:10.1039/C9SC03857D

Hydrocarbon-soluble, hexaanionic fulleride complexes of magnesium

Samuel Lawrence, C. André Ohlin, David B. Cordes, Alexandra M. Z. Slawin, Andreas Stasch^*

^*Corresponding author for this work

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

Abstract

The reaction of the magnesium(I) complexes [{(^Arnacnac)Mg}₂], (^Arnacnac = HC(MeCNAr)₂, Ar = Dip (2,6-iPr₂C₆H₃), Dep (2,6-Et₂C₆H₃), Mes (2,4,6-Me₃C₆H₂), Xyl (2,6-Me₂C₆H₃)) with fullerene C₆₀ afforded a series of hydrocarbon-soluble fulleride complexes [{(^Arnacnac)Mg}_nC₆₀], predominantly with n = 6, 4 and 2. ¹³C{¹H} NMR spectroscopic studies show both similarities (n = 6) and differences (n = 4, 2) to previously characterised examples of fulleride complexes and materials with electropositive metal ions. The molecular structures of [{^(Arnacnac)Mg}_nC₆₀] with n = 6, 4 and 2 can be described as inverse coordination complexes of n [(^Arnacnac)Mg]⁺ ions with C₆₀^n-anions showing predominantly ionic metal-ligand interactions, and include the first well-defined and soluble complexes of the C₆₀^6- ion. Experimental studies show the flexible ionic nature of the {(^Arnacnac)Mg}⁺∙∙∙∙C₆₀^6-coordination bonds. DFT calculations on the model complex [{(^Menacnac)Mg}₆C₆₀] (^Menacnac = HC(MeCNMe)₂) support the formulation as an ionic complex with a central C₆₀^6- anion and comparable frontier orbitals to C₆₀^6- with a small HOMO-LUMO gap. The reduction of C₆₀ to its hexaanion gives an indication about the reducing strength of dimagnesium(I) complexes.

Original language	English
Pages (from-to)	10755-10764
Number of pages	10
Journal	Chemical Science
Volume	10
Issue number	46
Early online date	9 Oct 2019
DOIs	https://doi.org/10.1039/C9SC03857D
Publication status	Published - 14 Dec 2019

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Copyright © 2019 The Author(s). Open Access Article. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
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@article{93f0db7c994c4dbab0ccd10b6efdd65c,

title = "Hydrocarbon-soluble, hexaanionic fulleride complexes of magnesium",

abstract = "The reaction of the magnesium(I) complexes [\{(Arnacnac)Mg\}2], (Arnacnac = HC(MeCNAr)2, Ar = Dip (2,6-iPr2C6H3), Dep (2,6-Et2C6H3), Mes (2,4,6-Me3C6H2), Xyl (2,6-Me2C6H3)) with fullerene C60 afforded a series of hydrocarbon-soluble fulleride complexes [\{(Arnacnac)Mg\}nC60], predominantly with n = 6, 4 and 2. 13C\{1H\} NMR spectroscopic studies show both similarities (n = 6) and differences (n = 4, 2) to previously characterised examples of fulleride complexes and materials with electropositive metal ions. The molecular structures of [\{(Arnacnac)Mg\}nC60] with n = 6, 4 and 2 can be described as inverse coordination complexes of n [(Arnacnac)Mg]+ ions with C60n- anions showing predominantly ionic metal-ligand interactions, and include the first well-defined and soluble complexes of the C606- ion. Experimental studies show the flexible ionic nature of the \{(Arnacnac)Mg\}+∙∙∙∙C606- coordination bonds. DFT calculations on the model complex [\{(Menacnac)Mg\}6C60] (Menacnac = HC(MeCNMe)2) support the formulation as an ionic complex with a central C606- anion and comparable frontier orbitals to C606- with a small HOMO-LUMO gap. The reduction of C60 to its hexaanion gives an indication about the reducing strength of dimagnesium(I) complexes.",

author = "Samuel Lawrence and Ohlin, \{C. Andr{\'e}\} and Cordes, \{David B.\} and Slawin, \{Alexandra M. Z.\} and Andreas Stasch",

note = "This work was supported by the University of St Andrews and the EPSRC (PhD studentship for SRL; EP/N509759/1). CAO thanks the Kempe Foundation for grant JCK-1719, and computational resources were provided by the High Performance Computing Centre North (HPC2N) and the National Supercomputer Centre (NSC) via grants SNIC 2018/3-253 and 2018/3-389, respectively.",

year = "2019",

month = dec,

day = "14",

doi = "10.1039/C9SC03857D",

language = "English",

volume = "10",

pages = "10755--10764",

journal = "Chemical Science",

issn = "2041-6520",

publisher = "Royal Society of Chemistry",

number = "46",

}

TY - JOUR

T1 - Hydrocarbon-soluble, hexaanionic fulleride complexes of magnesium

AU - Lawrence, Samuel

AU - Ohlin, C. André

AU - Cordes, David B.

AU - Slawin, Alexandra M. Z.

AU - Stasch, Andreas

N1 - This work was supported by the University of St Andrews and the EPSRC (PhD studentship for SRL; EP/N509759/1). CAO thanks the Kempe Foundation for grant JCK-1719, and computational resources were provided by the High Performance Computing Centre North (HPC2N) and the National Supercomputer Centre (NSC) via grants SNIC 2018/3-253 and 2018/3-389, respectively.

PY - 2019/12/14

Y1 - 2019/12/14

N2 - The reaction of the magnesium(I) complexes [{(Arnacnac)Mg}2], (Arnacnac = HC(MeCNAr)2, Ar = Dip (2,6-iPr2C6H3), Dep (2,6-Et2C6H3), Mes (2,4,6-Me3C6H2), Xyl (2,6-Me2C6H3)) with fullerene C60 afforded a series of hydrocarbon-soluble fulleride complexes [{(Arnacnac)Mg}nC60], predominantly with n = 6, 4 and 2. 13C{1H} NMR spectroscopic studies show both similarities (n = 6) and differences (n = 4, 2) to previously characterised examples of fulleride complexes and materials with electropositive metal ions. The molecular structures of [{(Arnacnac)Mg}nC60] with n = 6, 4 and 2 can be described as inverse coordination complexes of n [(Arnacnac)Mg]+ ions with C60n- anions showing predominantly ionic metal-ligand interactions, and include the first well-defined and soluble complexes of the C606- ion. Experimental studies show the flexible ionic nature of the {(Arnacnac)Mg}+∙∙∙∙C606- coordination bonds. DFT calculations on the model complex [{(Menacnac)Mg}6C60] (Menacnac = HC(MeCNMe)2) support the formulation as an ionic complex with a central C606- anion and comparable frontier orbitals to C606- with a small HOMO-LUMO gap. The reduction of C60 to its hexaanion gives an indication about the reducing strength of dimagnesium(I) complexes.

AB - The reaction of the magnesium(I) complexes [{(Arnacnac)Mg}2], (Arnacnac = HC(MeCNAr)2, Ar = Dip (2,6-iPr2C6H3), Dep (2,6-Et2C6H3), Mes (2,4,6-Me3C6H2), Xyl (2,6-Me2C6H3)) with fullerene C60 afforded a series of hydrocarbon-soluble fulleride complexes [{(Arnacnac)Mg}nC60], predominantly with n = 6, 4 and 2. 13C{1H} NMR spectroscopic studies show both similarities (n = 6) and differences (n = 4, 2) to previously characterised examples of fulleride complexes and materials with electropositive metal ions. The molecular structures of [{(Arnacnac)Mg}nC60] with n = 6, 4 and 2 can be described as inverse coordination complexes of n [(Arnacnac)Mg]+ ions with C60n- anions showing predominantly ionic metal-ligand interactions, and include the first well-defined and soluble complexes of the C606- ion. Experimental studies show the flexible ionic nature of the {(Arnacnac)Mg}+∙∙∙∙C606- coordination bonds. DFT calculations on the model complex [{(Menacnac)Mg}6C60] (Menacnac = HC(MeCNMe)2) support the formulation as an ionic complex with a central C606- anion and comparable frontier orbitals to C606- with a small HOMO-LUMO gap. The reduction of C60 to its hexaanion gives an indication about the reducing strength of dimagnesium(I) complexes.

UR - https://www.scopus.com/pages/publications/85075338385

U2 - 10.1039/C9SC03857D

DO - 10.1039/C9SC03857D

M3 - Article

SN - 2041-6520

VL - 10

SP - 10755

EP - 10764

JO - Chemical Science

JF - Chemical Science

IS - 46

ER -

Hydrocarbon-soluble, hexaanionic fulleride complexes of magnesium

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