Startseite Naturwissenschaften Synthesis and structure of bis(m-terphenyl)zinc (2,6-Mes2 C6 H3)2 Zn
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Synthesis and structure of bis(m-terphenyl)zinc (2,6-Mes2 C6 H3)2 Zn

  • Artem Schröder , Enno Lork und Jens Beckmann EMAIL logo
Veröffentlicht/Copyright: 17. September 2014
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Main Group Metal Chemistry
Aus der Zeitschrift Main Group Metal Chemistry Band 37 Heft 5-6

Abstract

The title compound bis(m-terphenyl)zinc (2,6-Mes2 C6 H3)2 Zn was obtained by the metathesis reaction of the lithium organyl 2,6-Mes2 C6 H3 Li with zinc difluoride ZnF2 and fully characterised by X-ray crystallography.

Keywords: homoleptic diarylmetal; X-ray structure determination; zinc

The beginning of organometallic chemistry is intimately related to the discovery of organozinc compounds such as Me2 Zn and Et2 Zn by Frankland in the mid-19th century (Seyferth, 2001). The handling of these pyrophoric compounds posed a substantial challenge at the time and required the development of hitherto unknown inert gas techniques. Despite being known for a long time, the structure of dialkylzinc compounds (Bacsa et al., 2011) and their hydrolysis/oxygenation products are still of current interest (Jana et al., 2007). This also holds true for diarylzinc compounds. Diphenylzinc is a dimer in the solid state (Markies et al., 1990), readily forms adducts with Lewis bases (e.g., pyridine or ethers) (Markies et al., 1992; Lennartson and Håkansson, 2009) and reacts with molecular oxygen to give phenylzinc phenolate (Lennartson and Håkansson, 2008). Diarylzinc compounds with bulkier substituents are monomers, show little tendency to form adducts and are substantially more stable towards oxidation. We prepared another member of this compound class, namely, (2,6-Mes2 C6 H3)2 Zn, by the reaction of 2,6-Mes2 C6 H3 Li with ZnF2, which was accidently present in a reaction mixture that was prepared to give a m-terphenylfluorosilane. After adjusting the reaction conditions, (2,6-Mes2 C6 H3)2 Zn was obtained as air-stable colourless crystals at a yield of 90% (Equation 1).

The molecular structure of (2,6-Mes2 C6 H3)2 Zn is shown in Figure 1. Selected geometrical parameters are collected in Table 1, along with known monomeric diarylzinc compounds for comparison.

Figure 1 Molecular structure of monoclinic (2,6-Mes2 C6 H3)2 Zn showing 30% probability ellipsoids and the crystallographic numbering scheme.
Figure 1

Molecular structure of monoclinic (2,6-Mes2 C6 H3)2 Zn showing 30% probability ellipsoids and the crystallographic numbering scheme.

Table 1

Selected geometrical parameters of monomeric diarylzinc compounds.

CompoundZn-C (Å)C-Zn-C (°)Approx. point group symmetryReferences
(C6 F5)2 Zn1.926(4), 1.930(5)172.5(2)Cs(Sun et al., 1998)
Mes2 Zn (monoclinic)1.942(2)180C2v(Cole et al., 2003)
Mes2 Zn (tetragonal)1.951(4)180C2v(Krieck et al., 2009)
[6-(CF3)C6 H4]2 Zn1.938(3), 1939(3)178.5(1)Cs(Chisholm et al., 2005)
[3,5-(CF3)2 C6 H3]2 Zn1.925(8), 1.938(8)177.0(2)C2v(Lai et al., 2012)
[2,4,6-(CF3)3 C6 H2]2 Zn1.949(3), 1.950(3)170.0(1)C2(Brooker et al., 1992)
(2,4,6-t-Bu3 C6 H2)2 Zn1.945(6)165.9(3)C2(Westerhausen et al., 2005)
(2,6-Naph2 C6 H3)2 Zn1.946(2), 1.955(2)168.27(9)Cs(Gridley et al., 2013)
[2,6-(2,6-Xyl)2 C6 H3]2 Zn1.944(4), 1.949(4)178.7(2)Cs(Blundell et al., 2014)
[2,6-(3,5-Xyl)2 C6 H3]2 Zn1.936(1), 1.940(1)171.18(5)Cs(Blundell et al., 2014)
[2,6-Pmp2 C6 H3]2 Zn1.939(3), 1.939(3)175.8(1)Cs(Blundell et al., 2014)
(2,6-Mes2 C6 H3)2 Zn1.945(3), 1.947(3)177.1(1)CsThis work

Like those of other bulky diarylzinc compounds, the spatial arrangement of the Zn atom of (2,6-Mes2 C6 H3)2 Zn is nearly linear (C-Zn-C 177.1(1)°) and the Zn-C bond lengths [1.945(3), 1.947(3)] are consistent. Differences are observed in the relative orientation of the phenyl rings. Like (C6 F5)2 Zn (Sun et al., 1998), [6-(CF3)C6 H4]2 Zn (Chisholm et al., 2005), the closely related (2,6-Naph2 C6 H3)2 Zn (Gridley et al., 2013), [2,6-(2,6-Xyl)2 C6 H3]2 Zn, [2,6-(3,5-Xyl)2 C6 H3]2 Zn, [2,6-Pmp2 C6 H3]2 Zn (Blundell et al., 2014) and the isoelectronic (2,6-Mes2 C6 H3)2 Hg (Niemeyer and Power, 1997), (2,6-Mes2 C6 H3)2 Zn adopts a nearly Cs symmetry, while Mes2 Zn (Cole et al., 2003; Krieck et al., 2009) and [3,5-(CF3)2 C6 H3]2 Zn (Lai et al., 2012) possess a nearly C2v symmetry. Presumably due to the large steric congestion, (2,4,6-t-Bu3 C6 H2)2 Zn (Westerhausen et al., 2005) and the related [2,4,6-(CF3)3 C6 H2]2 Zn (Brooker et al., 1992) approach only C2 symmetry. We currently investigated the use of (2,6-Mes2 C6 H3)2 Zn as a transmetallation reagent.

Experimental

To a solution of 2,6-Mes2 C6 H3 Li (500 mg, 1.56 mmol) in diethyl ether (10 mL) at -78°C, a suspension of ZnF2 (81 mg, 0.78 mmol) in diethyl ether (10 mL) was added. After 2 h, the mixture was warmed up to room temperature and stirred for an additional 12 h. The mixture was filtered and the volatile materials were removed under reduced pressure. Recrystallisation of the residue from n-hexane/CH2 Cl2 afforded colourless crystals of (2,6-Mes2 C6 H3)2 Zn (0.488 g, 0.71 mmol, 90%; Mp. 122°C).

1H NMR (CDCl3): δ=7.48 (t, 3J(1H,1H)=7.6 Hz, 2H), 7.12 (d, 3J(1H,1H)=7.6 Hz, 4H), 6.97 (s, 8H), 2.35 (s, 12H), 2.07 (s, 24H). 13C{1H} NMR (CDCl3): δ=141.3, 139.2, 136.6, 136.0, 130.4, 128.6, 128.2, 127.7, 21.2, 20.9. Anal. Calcd. for C48 H50 Zn (692.31): C, 83.28; H, 7.28. Found: C, 83.31; H, 7.11.

Crystallography

Single crystals of (2,6-Mes2 C6 H3)2 Zn·CHCl3 were obtained by crystallisation from CHCl3 at room temperature. Intensity data were collected on a Bruker Venture D8 diffractometer at 173 K with graphite-monochromated Mo-Kα (0.7107 Å) radiation. The structure was solved by direct methods and difference Fourier synthesis using SHELXS-97 and SHELXL-97 implemented in the program WinGX 2002 (Farrugia, 1999). Full-matrix least-squares refinements on F2, using all data. The absolute configuration was established by refinement of the Flack parameter [0.418(9)] (Flack, 1983). All non-hydrogen atoms were refined using anisotropic displacement parameters. Hydrogen atoms attached to carbon atoms were included in geometrically calculated positions using a riding model. Crystal and refinement data are collected in Table 2. Figures were created using the DIAMOND software (Brandenburg and Putz, 2006). Crystallographic data (excluding structure factors) for the structural analyses have been deposited with the Cambridge Crystallographic Data Centre (CCDC no. 1007854). Copies of this information may be obtained free of charge from The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: +44-1223-336033; e-mail: or http://www.ccdc.cam.ac.uk).

Table 2

Crystal data and structure refinement of (2,6-Mes2 C6 H3)2 Zn·CHCl3.

FormulaC49 H51 Cl3 Zn
Formula weight, g/mol811.62
Crystal systemMonoclinic
Crystal size, mm0.1×0.1×0.1
Space groupP21
a, Å10.008(5)
b, Å17.134(5)
c, Å12.567(5)
α, °90.00
β, °101.379(5)
γ, °90.00
V, Å32112(2)
Z2
ρcalcd, mg/m31.276
T, K173
μ (Mo Kα), mm-10.144
F(000)852
θ range, °2.38–26.59
Index ranges-12≤h≤10
-21≤k≤21
-15≤l≤15
No. of reflections collected24,651
Completeness to θmax99.8%
No. of independent reflections8747
No. of observed reflections with [I>2σ(I)]7872
No. of refined parameters490
GooF (F2)1.037
R1 (F) [I>2σ(I)]0.0413
wR2 (F2) (all data)0.0943
(Δ/σ)max<0.001
Largest difference peak/hole, e/Å-30.701/-0.360

GooF, goodness of fit.

Corresponding author: Jens Beckmann, Institut für Anorganische Chemie, Universität Bremen, Leobener Straße, D-28359 Bremen, Germany, e-mail:

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Received: 2014-7-4
Accepted: 2014-8-14
Published Online: 2014-9-17
Published in Print: 2014-12-1

©2014 by De Gruyter

This article is distributed under the terms of the Creative Commons Attribution Non-Commercial License, which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.

Artikel in diesem Heft

  1. Frontmatter
  2. Research Articles
  3. Synthesis and structure of an acyclic dialkylstannylene
  4. Two in one: the bismuth bromido clusters in [Bi6Cp*6Br9][Bi7Br24]
  5. 2D Hydrogen-bonded polymer assembled by zinc(II) tetraaza macrocyclic complex and 1,2-cyclopentanedicarboxylic acid
  6. An efficient synthesis of N-substituted pyrroles catalyzed by MgI2 etherate
  7. Synthesis and characterization of N2S2-tin macrocyclic complexes of Co(II), Ni(II), Cu(II) and Zn(II)
  8. Synthesis, characterization and in vitro cytotoxic activity of bis(triorganotin) 2,6-pyridinedicarboxylates
  9. Short Communications
  10. Reactivity of a spirobis(pentagerma[1.1.1]propellane)
  11. A monoclinic polymorph of 2,6-Mes2 C6 H3 SiF3
  12. Synthesis and structure of bis(m-terphenyl)zinc (2,6-Mes2 C6 H3)2 Zn
  13. Synthesis and structure of diarylhalotelluronium hexahalotellurates [(8-Me2 NC10 H6)2 TeX]2 TeX6 (X=Cl, Br)
  14. Synthesis and structure of three molecular arylindium phosphinates
  15. Molecular structure of Te2 Mg2(μ3-Cl2)(μ2-Cl4)Cl6(THF)4·CH2 Cl2
https://doi.org/10.1515/mgmc-2014-0021
Schlagwörter für diesen Artikel
homoleptic diarylmetal; X-ray structure determination; zinc
Creative Commons
BY-NC-ND 3.0

Artikel in diesem Heft

  1. Frontmatter
  2. Research Articles
  3. Synthesis and structure of an acyclic dialkylstannylene
  4. Two in one: the bismuth bromido clusters in [Bi6Cp*6Br9][Bi7Br24]
  5. 2D Hydrogen-bonded polymer assembled by zinc(II) tetraaza macrocyclic complex and 1,2-cyclopentanedicarboxylic acid
  6. An efficient synthesis of N-substituted pyrroles catalyzed by MgI2 etherate
  7. Synthesis and characterization of N2S2-tin macrocyclic complexes of Co(II), Ni(II), Cu(II) and Zn(II)
  8. Synthesis, characterization and in vitro cytotoxic activity of bis(triorganotin) 2,6-pyridinedicarboxylates
  9. Short Communications
  10. Reactivity of a spirobis(pentagerma[1.1.1]propellane)
  11. A monoclinic polymorph of 2,6-Mes2 C6 H3 SiF3
  12. Synthesis and structure of bis(m-terphenyl)zinc (2,6-Mes2 C6 H3)2 Zn
  13. Synthesis and structure of diarylhalotelluronium hexahalotellurates [(8-Me2 NC10 H6)2 TeX]2 TeX6 (X=Cl, Br)
  14. Synthesis and structure of three molecular arylindium phosphinates
  15. Molecular structure of Te2 Mg2(μ3-Cl2)(μ2-Cl4)Cl6(THF)4·CH2 Cl2
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