Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
found: C 38.24, H 4.76, N 4.50%. 1H NMR (400 MHz, CDCl3, mal parameters constraint to the thermal parameters of the binding
21 °C): δ = 2.22 (s, 6 H, 4-CH3), 2.51 (s, 12 H, N–CH3), 2.65 (s, 4 H, carbon atoms. The model refined for 4 includes a 70:30 disorder of a
major part of the structure. The final refinements converged to wR2 =
8.00 Hz, 4 H, CHarom). 13C NMR (101 MHz, CDCl3, 21 °C): δ = 21.0, 0.1568 (1), 0.1273 (2), 0.0981 (3), and 0.1339 (4) (F2, all data) and
3
3
N–CH2), 6.75 (d, JC,H = 8.00 Hz, 4 H, CHarom.), 7.67 (d, JC,H
=
48.9, 57.1, 101.3, 129.3, 134.8, 140.9. 125Te NMR (126 MHz, CDCl3,
21 °C): δ = –278.77 (s). IR (KBr): ν˜ = 3002, 2991, 2975, 2966, 2929,
2916, 2881, 2862, 2848, 2804, 1568, 1482, 1461, 1430, 1409, 1345,
1297, 1285, 1279, 1260, 1239, 1208, 1119, 1111, 1104, 1098, 1055,
1038, 1019, 1009, 951, 924, 841, 797, 764, 737, 699, 668, 585, 481,
443 cm–1. UV/Vis (in dichloromethane) λmax = 232, 251 nm.
R1 = 0.0553 (1), 0.0503 (2), 0.0361 (3), and 0.0570 (4) [F, 3742 (1),
2369 (2) and 6395 (3), and 2809 (4) reflections with I Ͼ 2σ(I)]. Crys-
tallographic data for complexes 2–4 are summarized in Table 1, the
ones for 1 have been deposited with CCDC.
Crystallographic data (excluding structure factors) for the structures in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
of the data can be obtained free of charge on quoting the depository
numbers CCDC-156929 [zinc(tmeda)diphenyltellurolato (1)] CCDC-
1852745 [zinc(tmeda)bis(4-methylphenyltellurolato) (2)], CCDC-
156930 [zinc(tmeda)bis(2,4,6-trimethylphenyltellurolato) (3)] and
CCDC-156932 [zinc(tmeda)bromo(phenyltellurolato) (4)] (Fax:
Data for Complex 3: White crystalline product (0.152 g, 0.225 mmol,
46%). M.p.: 164–165 °C (with decomposition starting at 150 °C).
C24H38N2Te2Zn: calcd. C 42.66, H 5.67, N 4.15%, found: C 41.96, H
5.41, N 3.92%. 1H NMR (400 MHz, CDCl3, 21 °C): δ = 2.16 (s, 6 H,
4-CH3), 2.38 (s, 12 H, 2,6-CH3), 2.56 (s, 12 H, N–CH3), 2.65 (s, 4 H,
N–CH2), 6.64 (s, 4 H, CHarom). 13C NMR (101 MHz, CDCl3, 21 °C):
δ = 20.7, 32.2, 49.2, 57.2, 112.2, 126.1, 134.7, 144.7. 125Te NMR
(126 MHz, CDCl3, 21 °C): δ = 306.79 (s). IR (KBr): ν˜ = 2995, 2958,
2912, 2883, 2848, 2802, 2717, 1738, 1709, 1591, 1543, 1537, 1457,
1370, 1263, 1248, 1240, 1181, 1169, 1098, 1063, 1009, 951, 856, 847,
811, 799, 768, 700, 579, 542, 488, 462, 441 cm–1. UV/Vis (in dichloro-
methane) λmax = 232, 251 nm.
+44-1223-336-033;
E-Mail:
deposit@ccdc.cam.ac.uk,
http://
www.ccdc.cam.ac.uk)
Reaction of Tin Tetrachloride and MTePh [M = Zn(tmeda)(TePh),
Li, Na, and Me3Si]: An inversion recovery NMR experiment was
used to optimize D1 so that the integrated ratio of tin tetra(phenyltellu-
rolato) to diphenylditelluride could be used to estimate product yields.
The optimized D1 value is long enough to allow the Boltzman popula-
tion to re-establish before the next 180° pulse. In the measurement the
recovery time D1 was varied and the intensity of the signal measured.
The spin-lattice relaxation time for the tin tetra(phenyltellurolato) in a
125Te NMR experiment is much shorter than for diphenylditelluride.
The maximum peak intensity of both tin tetra(phenyltellurolato) and
diphenylditelluride was reached with D1 of 6.4 s and a PW of
11.5 μs.
Preparation of Zinc(tmeda)bromo(phenyltellurolato) (4): Sodium
borohydride (0.076 g, 2.0 mmol) in ethanol (10 mL) was added to a
solution of diphenylditelluride (0.41 g, 1.0 mmol) in ethanol (10 mL)
at 21 °C. The resultant pale yellow solution was added to a white
suspension of zinc(tmeda)dibromo (0.68 g, 2.0 mmol) in ethanol
(40 mL) under vigorous stirring at –78 °C. After slowly warming the
white suspension to 21 °C, stirring was continued overnight, volatiles
were removed in vacuo, the residue extracted with toluene (2ϫ25 mL)
and filtered through Celite. The pale yellow filtrate was stored at
–15 °C. After 48 h clear white crystals of zinc(tmeda)bromo(phenyl-
tellurolato) developed in the solution, which were collected by
filtration, washed with cold ethanol (10 mL, –20 °C), dried under vac-
uum and taken into an argon atmosphere box: (0.57 g, 1.3 mmol,
65%). On exposure to air the crystals become orange after ca. 5 min.
Colorless crystalline product, mp: 112–114 °C (the melt was orange).
C12H21BrN2TeZn: calcd. C 30.89; H 4.54; N 6.01%, found: C 31.56;
(a) Reaction of Tin Tetrachloride and Complex 1: In an inert atmo-
sphere ethanol (20 mL) and toluene (5 mL) were added to zinc-
(tmeda)bis(phenyltellurolate) (0.59 g, 1.0 mmol). A pale yellow solu-
tion developed, to which a solution of tin tetrachloride (0.13 g,
0.50 mmol) in ethanol (15 mL) was added dropwise to this mixture at
–78 °C. The reaction mixture was warmed to 21 °C and stirred for
additional 30 min resulting in an orange-red solution and red crystal-
line needles. Volatiles were removed in vacuo, the red-orange solids
dissolved in diethyl ether (2ϫ25 mL) and filtered to remove a yellow
residue. A sample of the solution was added to [D]chloroform and the
125Te NMR spectra recorded revealing tin tetra(phenyltellurolate) as
the only tellurium containing product in solution. The synthesis was
repeated and the red needles formed in the reaction mixture were col-
lected by filtration, dried under vacuum to yield tin tetra(phenyltellur-
olate) (0.44 g, 0.47 mmol, 93%). M.p.: 87 °C (ethanol), C24H20SnTe4:
calcd. C 30.71; H 2.15; N 0.00%; found: C 30.28; H 2.10; N 0.00%.
1H NMR (400 MHz, C6D5CD3, 21 °C): δ = 6.85 (tr, 2 H); 6.98 (m, 1
H); 7.57 (d, 2 H) ppm. 13C NMR (101 MHz, C6D5CD3, 21 °C): δ
1
H 4.75; N 5.92%. H NMR (400 MHz, CDCl3, 21 °C): δ = 2.62 (s,
3
12 H, CH3), 2.71 (s, 4 H, CH2), 6.96 (t, JC,H = 7.6 Hz, 4 H, CHarom),
3
3
7.12 (t, JC,H = 7.6 Hz, 2 H, CHarom), 7.88 (d, JC,H = 7.6 Hz, 4 H,
CHarom). 13C NMR (101 MHz, CDCl3, 21 °C): δ = 48.6, 56.9, 125.4,
128.4, 140.9. 13C NMR (solid state): δ = 47.13 ppm, 56.72 ppm (very
small peak), 111.45, 128.19, 131.5, 139.68. 125Te NMR (126 MHz,
CDCl3, 21 °C): δ = –311.26, –257.67. IR (KBr): ν˜ = 1567, 1463, 1353,
1287, 1262, 1243, 1194, 1173, 1125, 1104, 1059, 1042, 1027, 1019,
1001, 949, 797, 764, 742, 695, 648, 587, 494, 455 cm–1.
Crystallographic Determination: Single crystals of the complexes
were obtained from saturated toluene solutions. The single crystals
selected for data collection were mounted with a trace of silicon oil
on a 0.1 mm glass capillary. X-ray diffraction data were collected with
a Siemens Smart platform diffractometer using three different φ set-
= 128.3; 129.4; 137.6; 141.6 ppm. 125Te NMR (126 MHz, C6D5CD3,
125
21 °C): δ = 271.17 ppm (J119, 117
= 3263 and 3289 Hz).
Te
Sn–
(b) Reaction of Tin Tetrachloride and Lithium Phenyltellurolate:
tings and 0.3° increment ω scans 2θ Ͻ 56.56° (1, Mo-Kα, 16,644 refl), In an inert atmosphere a solution of phenyllithium [0.56 mL, 1.8
39.00° (2, Ag-Kα, 19,630 refl), and 74.22° (3, Ag-Kα, 84,980 refl), and mol·L–1, 1 mmol in cyclohexane-ether (70:30)] was added to a suspen-
56.56° (4, Mo-Kα, 10,878 refl). Corrections for absorption and decay sion of tellurium powder (0.128 g, 1 mmol) in tetrahydrofuran (15 mL)
were applied using SADABS.[35] Solution by direct methods using
at 21 °C. The reaction mixture was stirred for 30 min to give a pale
SHELXS-86[36] and refinement by full-matrix least-squares on F2 green solution with small amounts of unreacted tellurium metal. This
using all 5991 (1), 3979 (2), 13598 (3), and 4029 (4) unique data using solution was added to a solution of tin tetrachloride (0.065 g,
SHELXL-93 and SHELXL-2017.[37] The final refinements included 0.25 mmol) in tetrahydrofuran (15 mL) at –78 °C, to give an orange-
anisotropic thermal displacement parameters for non-hydrogen atoms
and hydrogen atoms calculated on idealized positions with their ther-
red solution containing a brown precipitate. Volatiles were removed in
vacuo, the orange solids dissolved in diethyl ether (2ϫ25 mL) and
Z. Anorg. Allg. Chem. 0000, 0–0
7
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim