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For reviews on dehydrogenative oligo- or polymerization of secondary stannanes, see: a) Organotin polymers and related materials: H. K. Sharma, K. H. Pannell in Tin Chemistry: Funct.amentals, Frontiers and Applications Eds.: A. G Davies, M. Gielen, K. H. Pannell, E. R. T. Tiekink, Wiley, New York, 2008, pp. 371-387;
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In a catalytic experiment, a 5 mm Pyrex NMR tube was charged with a mixture of t Bu2SnH2 (0.5-1.0 mmol) and 3-5 mol, of catalyst in 1.0 mL of degassed C6D6, and the tube was flame-sealed under vacuum. The sealed NMR tube was either irradiated with a 450 W medium-pressure mercury lamp at roomtemperature or suspended in an oil bath at 60°C, and the reaction was periodically monitored by 1H, 13C, and 119Sn NMR spectroscopy. After completion of the reaction, distannane 2 was separated from the catalyst by flash chromatography in hexanes and was isolated in 80-90% yield. Caution: When breaking the seal of the NMR tube, sometimes the tube shattered with a minor explosion. Therefore, it is recommended to cool the NMR tube in liquid N 2 before breaking the seal, b) Photolysis of t Bu 2SnH2 in benzene in the absence of the catalyst for 24 h produced dist
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2 in benzene in the absence of the catalyst for 24 h produced distannane 2 in 1 % yield.
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70349946909
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119Sn NMR spectral changes associated with the conversion of 1 to 2 in the presence of catalyst 4 are presented in Figure 1 of the Supporting Information.
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119Sn NMR spectral changes associated with the conversion of 1 to 2 in the presence of catalyst 4 are presented in Figure 1 of the Supporting Information.
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For the synthesis and spectral data of 7 and 8, see the Supporting Information.
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For the synthesis and spectral data of 7 and 8, see the Supporting Information.
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70349956221
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Single crystals of 7 or 8 were mounted on a Bruker APEX CCD diffractometer equipped with monochromatic MoKα radiation. Data collection was done with SMART [G M. Sheldrick, SMART Bruker AXS, Madison, WI, USA, 2000, Cell refinement, data reduction, and incident beam and decay corrections were carried out with SAINT-Plus [G. M. Sheldrick, SAINT-Plus 6.23c Bruker AXS, Madison, WI, USA, 2000, The structure was solved by direct methods and refined by full-matrix least-squares techniques in SHELXTL [G. M. Sheldrick, SHELXTL 6.10 Bruker AXS, Madison, WI, USA, 2000, Hydrogen atoms were generated in calculated positions and constrained with the use of a riding model with the exception of the hydride that was located in the difference Fourier map. Crystal data for 7: C32H39FeOPSn, M, 645.14, space group P 1̄, a, 10.60(2, b, 11.80(3, c, 13.26(3) Å, a, 93.744, β
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int = 0.0365]. Completeness to 2θ = 52.70°: 99.3%. R 1 = 0.0313, wR 2 = 0.1101 [I>2σ(I)]. CCDC 723088 (7) and CCDC 734347 (8) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data-request/cif.
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