The 1,3-Sn2O2-Heterocycle as a Ligand in Organometallic Compounds
FULL PAPER
Madach, H. Vahrenkamp, Z. Naturforsch.
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1 cm) which were brought into a Schlenk tube (250 ml). Diethyl
ether (30 ml), within the tube, was allowed to diffuse through the
gas phase into the THF solution (3 h). After this period of time
the diethyl ether was replaced by petroleum ether (boiling range
40Ϫ60°C) (50 ml). Vapor diffusion of the petroleum ether (10 d)
yielded yellow single crystals suitable for X-ray structure analysis.
1195Ϫ1198.
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For reviews see:
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For more recent publications on “inidene” compounds [LnM
…E(X)…ML ]n see also: E ϭ In, Tl: [7a] O. J. Curnow, B. Schie-
Ϫ
Ϫ
n
menz, G. Huttner, L. Zsolnai, J. Organomet. Chem. 1993, 459,
[7b]
Crystalline yield: 110 mg; 11%. M.p. 166°C (dec.). Ϫ IR (THF):
17Ϫ20. Ϫ E ϭ Ge:
B. Schiemenz, G. Huttner, Chem. Ber.
˜
νCO ϭ 2037 (w), 2001 (s), 1917 (vs), 1889 (s) cmϪ1. Ϫ UV/Vis
1994, 127, 2129Ϫ2133. Ϫ E ϭ Sn: See ref.[4]. Ϫ E ϭ Pb:
F.
[7c]
(THF): λ (lg ε) ϭ 309 (4.45), 357 (3.98). Ϫ 1H NMR for
[Na(solv)x]·3 ([D6]acetone, 25°C): δ ϭ 8.04 (d, 1 H, H5), 6.73 (d,
1 H, H6), 2.44 (s, 3 H, H7) (numbers refer to Figure 1). Ϫ 13C
NMR for [Na(solv)x]·3 ([D6]acetone, 25°C): δ ϭ 229.8 (s, CCOax),
222.6 (s, CCOeq), 177.6 (C1), 156.0 (C5), 155.3 (C2), 153.7 (C3),
111.5 (C6), 15.3 (C7) (numbers as given in Figure 1). Ϫ 119Sn NMR
for [Na(solv)x]·3 ([D6]acetone, 25°C): δ ϭ 1361. Ϫ [Na(12-Crown-
4)2]·3, C32H37Cr2NaO21Sn (1003.3): calcd. C 38.31, H 3.72; found
C 38.37, H 3.85.
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X-ray Structure Determinations: The measurements for
[nBu4N]2 ·1a, [Ph4P]2 ·1a, [Ph4P]2 ·1c, and [Na(12-Crown-4)2]·3
were carried out with a Siemens P4 four-circle diffractometer with
graphite-monochromated Mo-Kα radiation. The intensities of three
check reflections (measured every 100 reflections) remained con-
stant (except for [nBu4N]·1a) throughout the data collection, thus
indicating crystal and electronic stability. All calculations were per-
formed using the SHELXT PLUS software package. Structures
were solved by direct methods with the SHELXS-86 program and
refined with the SHELX93 program.[23] The program XPMA[24]
was used for graphical handling of the data. Absorption correc-
tions (ψ scan, ∆ψ ϭ 10°) were applied to the data. The structures
were refined in fully or partially anisotropic models by full-matrix
least-squares calculations. Hydrogen atoms were introduced at cal-
culated positions. Table 5 compiles the data for the structure deter-
minations. Peculiarities about the structure of [Na(12-Crown-4)2]·3
are the following: One of the crown ether molecules shows disorder
and could only be refined isotropically.
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tained from the Fachinformationszentrum Karlsruhe, D-76344
Eggenstein-Leopoldshafen (Germany), on quoting the depository
numbers CSD-408368 ([nBu4N]2 ·1a), -408369 ([Ph4P]2 ·1a),
-408367 ([Ph4P]2 ·1c), -408370 ([Na(12-Crown-4)2]·3).
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