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Main Group Metal Chemistry

Editor-in-Chief: Jurkschat, Klaus

Editorial Board: Atwood, David / Basu Baul, Tushar S. / Beckmann, Jens / Chandrasekhar, Vadepalli / Izod, Keith / Jones, Cameron / Karlov, Sergey S. / Mehring, Michael / Molloy, Kieran / Naseer, Muhammad Moazzam / Ramasami, Ponnadurai / Ruhlandt-Senge, Karin / Ruzicka, Ales / Saito, Masaichi / Sarazin, Yann / Tokitoh, Norihiro / Wagler, Jörg


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Volume 36, Issue 3-4

Issues

Synthesis of 7,7,14,14-tetrachlorodinaphtho[1,8bc:1′,8′-fg][1,5]distannocine. Molecular structure of the di-water tetra-THF adduct

Jens Beckmann
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  • Institute for Inorganic Chemistry, Bremen University, Leobener Straße, D-28359 Bremen, Germany
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/ Emanuel Hupf
  • Institute for Inorganic Chemistry, Bremen University, Leobener Straße, D-28359 Bremen, Germany
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/ Enno Lork
  • Institute for Inorganic Chemistry, Bremen University, Leobener Straße, D-28359 Bremen, Germany
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Published Online: 2013-05-18 | DOI: https://doi.org/10.1515/mgmc-2013-0022

Abstract

The salt metathesis reaction of 1,8-dilithionaphthalene with tributyltin chloride provided 1,8-bis(tributyltin)naphthalene (1) in 41% yield. The transmetallation of 1 with tin tetrachloride gave rise to the formation of 7,7,14,14-tetrachlorodinaphtho[1,8bc:1′,8′-fg][1,5]distannocine (2) in 75% yield. The molecular structure of 2·2 H2O·4 THF was established by single crystal X-ray crystallography.

Keywords: hypercoordination; tin; transmetallation

1,8-Bis(trimethylstannyl)naphthalene (I) is a prominent example of a compound in which two bulky substituents situated in the peri-position impose strain on each other. This strain is relieved by repulsion, in- and out-of-plane deflection, as well as distortion or buckling of the aromatic ring system (Seyferth and Vick, 1977; Blount et al., 1980). Owing to the quite labile Sn-Carom. bonds, I has also been used as starting material in transmetallation reactions with Lewis acids such as Me2SnCl2 (Altmann et al., 1998), BCl3 (Schulte and Gabbaï, 2002), GaCl3 (Hoefelmeyer et al., 2001a), and InCl3 (Hoefelmeyer et al., 2001b) for the preparation of further peri-substituted naphthalenes.

Amongst these, heterocycles IIV containing two 1,8-naphthyl moieties and two main group elements, e.g., Ga, In and Sn, were obtained (Scheme 1). The synthesis of I involves a salt metathesis reaction of 1,8-dilithionaphthalene with trimethyltin chloride.

1,8-Bis(trimethylstannyl)naphthalene (I) and transmetallation products II–V.
Scheme 1

1,8-Bis(trimethylstannyl)naphthalene (I) and transmetallation products IIV.

The preparation of trimethyltin chloride is quite tedious and costly, which is also reflected in the prices of commercial suppliers. Therefore, we were invoked in the preparation of a cheaper alternative of I, namely, 1,8-bis(tributylstannyl)naphthalene (1), which was prepared in an analogous way from 1,8-dilithionaphthalene and the inexpensive commercially available tributyltin chloride (Scheme 2). Compound 1 was isolated as colourless air-stable oil in 41% yield. In an effort to verify synthetic utility, the transmetallation reaction of 1 with tin tetrachloride was carried out, which provided 7,7,14,14-tetrachloro-dinaphtho[1,8bc:1′,8′-fg][1,5]distannocine (2) as sole product in 75% yield (Scheme 2).

Synthesis of 1,8-bis(tributylstannyl)naphthalene (1) and 7,7,14,14-tetrachloro-dinaphtho[1,8bc:1′,8′-fg][1,5]distannocine (2).
Scheme 2

Synthesis of 1,8-bis(tributylstannyl)naphthalene (1) and 7,7,14,14-tetrachloro-dinaphtho[1,8bc:1′,8′-fg][1,5]distannocine (2).

Compound 2 precipitated from the reaction mixture as microcrystalline material that was almost insoluble in all common solvents. Attempts to recrystallise 2 from THF containing a small amount of water provided colourless single crystals of the aqua complex 2·2 H2O, as its THF solvate 2·2 H2O·4 THF, which was studied by single crystal X-ray crystallography. The molecular structure is shown in Figure 1. Selected bond parameters are collected in the caption, whereas crystal and refinement data are listed in Table 1.

Molecular structure of 2·2 H2O·4 THF showing 30% probability ellipsoids and the crystallographic numbering scheme (symmetry operation used to generate equivalent atoms: a=-y, -x, 1-z). Selected geometrical parameters [Å, °]: Sn1-Cl1 2.4054(8), Sn1-Cl2 2.413(1), Sn1-O1a 2.486(2), Sn1-O1 2.516(2), Sn1-C10 2.134(3), Sn1-C18a 2.136(3), C10-Sn1-C18a 155.85(9), C10-Sn1-Cl1 98.46(7), C18a-Sn1-Cl1 99.08(7), C10-Sn1-Cl2 98.10(6), C18a-Sn1-Cl2 97.33(7), Cl1-Sn1-Cl2 93.30(3), C10-Sn1-O1a 82.05(8), C18a-Sn1-O1a 82.26(8), Cl1-Sn1-O1a 87.51(5), Cl2-Sn1-O1a 179.14(5), C10-Sn1-O1 81.69(8), C18a-Sn1-O1 80.84(8), Cl1-Sn1-O1 179.75(5), Cl2-Sn1-O1 86.47(5), O1-Sn1-O1a 92.72(6), peri-region distance Sn1···Sn1a 3.452(1), peri-region bond angles Sn1-C10-C19 128.7(3), C10-C19-C18 125.9(2), Sn1a-C18-C19 129.5(3), Σ of bay angles 384.1(8), splay angle 24.1, out-of-plane displacement Sn1 -0.0476(2) and Sn1a 0.0232(2), central naphthalene ring torsion angles C13-C14-C19-C18 179.6(3), C15-C14C-19-C10 178.7(3). Numbers in parantheses indicate standard deviations.
Figure 1

Molecular structure of 2·2 H2O·4 THF showing 30% probability ellipsoids and the crystallographic numbering scheme (symmetry operation used to generate equivalent atoms: a=-y, -x, 1-z). Selected geometrical parameters [Å, °]: Sn1-Cl1 2.4054(8), Sn1-Cl2 2.413(1), Sn1-O1a 2.486(2), Sn1-O1 2.516(2), Sn1-C10 2.134(3), Sn1-C18a 2.136(3), C10-Sn1-C18a 155.85(9), C10-Sn1-Cl1 98.46(7), C18a-Sn1-Cl1 99.08(7), C10-Sn1-Cl2 98.10(6), C18a-Sn1-Cl2 97.33(7), Cl1-Sn1-Cl2 93.30(3), C10-Sn1-O1a 82.05(8), C18a-Sn1-O1a 82.26(8), Cl1-Sn1-O1a 87.51(5), Cl2-Sn1-O1a 179.14(5), C10-Sn1-O1 81.69(8), C18a-Sn1-O1 80.84(8), Cl1-Sn1-O1 179.75(5), Cl2-Sn1-O1 86.47(5), O1-Sn1-O1a 92.72(6), peri-region distance Sn1···Sn1a 3.452(1), peri-region bond angles Sn1-C10-C19 128.7(3), C10-C19-C18 125.9(2), Sn1a-C18-C19 129.5(3), Σ of bay angles 384.1(8), splay angle 24.1, out-of-plane displacement Sn1 -0.0476(2) and Sn1a 0.0232(2), central naphthalene ring torsion angles C13-C14-C19-C18 179.6(3), C15-C14C-19-C10 178.7(3). Numbers in parantheses indicate standard deviations.

Table 1

Crystal data and structure refinement of 2·2 H2O·4 THF.

The spatial arrangement of the Sn atoms of 2·2 H2O·4 THF is distorted octahedral and is defined by a C2Cl2+O2 donor set (coordination number 4+2). The distortion is reflected in the putative linear C-Sn-C bond angle that is narrowed to 155.85(9)°. The related C-Sn-C angle of II [126.6(6)° and 127.5(6)°] is even shorter due to the lower coordination number of the distorted tetrahedral Sn atoms (Meinwald et al., 1977). The coordination of the two water molecules in 2·2 H2O·4 THF gives rise to Sn···O bond lengths [2.486(2) Å and 2.516(2) Å] that are slightly longer than those of other organotin chloride water adducts, such as (Me3SiCH2)2SnCl2·H2O [2.404(8) Å] (Beckmann et al., 2002) and 2,6-Mes2C6H3SnCl2(OH)·H2O [2.316(4) Å] (Ahmad et al., 2010), presumably due to the lower coordination number of the Sn atoms (CN=4+1) in the latter reference compounds. To the best of our knowledge, this is the first reported case in which a μ2-O atom of a water molecule bridges two Sn atoms. The two water molecules are associated to four THF molecules by hydrogen bonding. The O···O donor acceptor distance [2.646(3) Å and 2.620(3) Å] is consistent with medium-strength hydrogen bonding. The non-bonding peri-distance of 2·2 H2O·4 THF [Sn···Sn 3.452(1) Å] is smaller than that in I [3.8640(4) Å] (Seyferth and Vick, 1977) and II (3.56 Å) (Meinwald et. al., 1977). The two Sn atoms are displaced from the naphthalene plane in a transoid fashion. The in- and out-of-plane displacement of the Sn atoms [-0.0476(2) Å and 0.0232(2) Å, respectively] is smaller than in I [-1.1032(1) Å and 1.0704(1) Å, respectively] (Seyferth and Vick, 1977). Overall, the repulsion between the Sn atoms of 2·2 H2O·4 THF appears less pronounced than in I and II. We suggest that the low solubility of water-free 2 is due to the intermolecular Sn···Cl interaction of adjacent molecules in the crystal lattice and the high lattice energy associated with this. The lattice energy might be higher than in other diaryltin dichlorides, e.g., Ph2SnCl2, as the high coordination number of the Sn atoms may relieve strain imposed by the peri-coordination, e.g., by going from a widened tetrahedral C-Sn-C angle such as present in II to a narrowed C-Sn-C angle as observed in 2·2 H2O·4 THF. Compounds IIV were prepared in the context of their ability to undergo complexation with small anions, such as fluoride. We speculate that 2 might be also useful for the binding of fluoride anions, the chemistry of which has received considerable attention in recent years (Perdikaki et al., 2002; Chaniotakis et al., 2004; Reeske et al., 2007, 2008; Wade et al., 2010; Zhao and Gabbaï, 2010; Dong et al., 2012; Cametti and Rissanen, 2013).

Experimental section

General

Starting materials (1-bromonaphthalene, n-butyllithium, tributyltin chloride, and tin tetrachloride) were obtained commercially (Sigma-Aldrich, Germany) and were used as received. Dry solvents were collected from an SPS800 mBraun solvent system. 1H-, 13C-, and 119Sn-NMR spectra were recorded at r.t. using a Bruker Avance-360 spectrometer and are referenced to tetramethylsilane (1H, 13C) and tetramethyltin (119Sn). Chemical shifts are reported in parts per million (ppm), and coupling constants (J) are given in Hertz (Hz).

Synthesis of 1,8-bis(tributylstannyl) naphthalene (SnBu3)2C10H6(1)

The preparation of 1,8-dilithionaphthalene was carried out according to a literature method (van Soolingen et al., 1995). A solution of n-butyllithium (15.0 mmol, 2.5 m in n-hexane) in diethyl ether (25 mL) was cooled to -20°C and 1-bromonaphthalene (2.59 g, 12.5 mmol) was added dropwise. The suspension was warmed to r.t. and stirred for a further 30 min. The mixture was cooled to -15°C and the solution was decanted. The resulting white precipitate was washed four times with n-hexane (25 mL). n-Butyllithium (16.5 mmol, 2.5 m in n-hexane) and N,N,N,N-tetramethylethylenediamine (2.03 g, 17.5 mmol) were added to the precipitate and stirred for 4 h under reflux. Diethyl ether (20 mL) was added at r.t. and the resulting suspension was cooled to -20°C. A solution of tributyltin chloride (10.2 g, 31.3 mmol) in diethyl ether (15 mL) was added dropwise. The mixture was stirred at -20°C for a further 60 min and was allowed to warm up to r.t. overnight. The suspension was extracted three times with water. The organic layer was separated and dried over magnesium sulphate and the solvent was removed by rotary evaporation. The resulting brownish-yellow oil was purified by Kugelrohr distillation at 300°C and 5.8·10-1 mbar to yield 3.60 g (10.2 mmol, 41%) of 1,8-bis(tributylstannyl)/naphthalene (1), as a yellow oil.

1H-NMR (CDCl3): δ=7.75 (m, 4H, H-2,4), 7.40 [t, 3J(1H-1H)=7 Hz, 2H, H-3], 1.50 (m, 12H, CH2-β), 1.37 (m, 12H, CH2-γ), 1.19 (m, 12H, CH2-α), 0.94 ppm [t, 3J(1H-1H)=7 Hz, 18H, CH3]. 13C{1H}-NMR (CDCl3): δ=146.0 [2J or 3J(119/117Sn-13C)=29 Hz, CA or CB], 144.7 [1J(119/117Sn-13C)=19 Hz, C1], 137.7 [2J(119/117Sn-13C)=22 Hz, C2], 134.2 [2J or 3J(119/117Sn-13C)=32 Hz, CA or CB], 129.5 (s, C4), 123.9 [3J(119/117Sn-13C)=48 Hz, C3], 29.0 [2J(119/117Sn-13C)=19 Hz, Cb], 27.4 [3J(119/117Sn-13C)=64 Hz, Cg], 13.6 (s, CH3), 13.0 ppm [1J(119/117Sn-13C)=334/318 Hz, Cα]. 119Sn{1H}-NMR (CDCl3): δ=-34.6 ppm (s).

Synthesis of 7,7,14,14-tetrachlorodinaphtho [1,8-bc:1′,8′-fg][1,5]distannocine (2)

Tin(IV) chloride (0.50 g, 1.92 mmol) was added dropwise to a solution of 1,8-bis(tributylstannyl)naphthalene (1) (0.50 g, 0.71 mmol) in n-hexane (5 mL) and was stirred at r.t. overnight. The white precipitate was allowed to settle and the supernatant solution was decanted. The precipitate was washed three times with n-hexane and dried in vacuo, affording 0.33 g (0.53 mmol, 75%) of 7,7,14,14-tetrachlorodinaphtho[1,8-bc:1′,8′-fg][1,5]distannocine (2).

119Sn{1H}-NMR (d8-THF): δ=-188.6 ppm (s, ω1/2=18 Hz) (acquired within 3d from saturated solution.

Recrystallisation of 2 (50.0 mg, 80.7 mmol) by THF (2 ml) and water (50 μL) yielded 2·2 H2O·4 THF as colourless crystals (25.4 mg, 26.9 mmol, 33%).

1H-NMR (THF-d8): δ=8.69 [d, 3J(1H-1H)=7 Hz, 2J(119/117Sn-1H)=121/107 Hz, 4H, H-2], 8.12 [d, 3J(1H-1H)=8 Hz, 4H, H-4], 7.73 ppm [t, 3J(1H-1H)=8 Hz, 4H, H-3]. 13C{1H}-NMR (THF-d8): δ=140.9 (s, C1), 136.8 (s, C2), 133.6 (s, C4), 127.2 ppm (s, C3). 119Sn{1H}-NMR (THF-d8): δ=-245.8 ppm (s, ω1/2=201 Hz).

X-ray crystallography

The intensity data of 2·2 H2O·4 THF were collected on a Siemens P4 diffractometer with graphite-monochromated Mo-Kα (0.7107 Å) radiation. Data were reduced and corrected for absorption (Walker and Stuart, 1983). The structure was solved by direct methods and difference Fourier synthesis with subsequent full-matrix least-squares refinements on F2, using all data (Sheldrick, 2008). 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 1. Figures were created using DIAMOND (Brandenburg and Putz, 2006). Crystallographic data (excluding structure factors) for the structural analysis have been deposited with the Cambridge Crystallographic Data Centre, CCDC number 933370. 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).

The Deutsche Forschungsgemeinschaft (DFG) is gratefully acknowledged for financial support.

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About the article

Corresponding author: Jens Beckmann, Institute for Inorganic Chemistry, Bremen University, Leobener Straße, D-28359 Bremen, Germany


Received: 2013-04-10

Accepted: 2013-04-16

Published Online: 2013-05-18

Published in Print: 2013-07-01


Citation Information: Main Group Metal Chemistry, Volume 36, Issue 3-4, Pages 145–149, ISSN (Online) 2191-0219, ISSN (Print) 0792-1241, DOI: https://doi.org/10.1515/mgmc-2013-0022.

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