Formation and Reactivity of Organo-Functionalized Tin Selenide Clusters.

Formation and Reactivity of Organo-Functionalized Tin Selenide Clusters.
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有机功能化硒化锡簇的形成和反应性。

DOI:
10.1002/chem.201503562
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发表时间:
2016
期刊:
影响因子:
--
通讯作者:
S. Dehnen
S. Dehnen
中科院分区:
--
文献类型:
--
作者:
Niklas Rinn;J. Eußner;Willy Kaschuba;Xiulan Xie;S. Dehnen

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R(1)SnCl3(R(1)=CMe2CH2C(O)Me)与(SiMe3)2Se反应生成了一系列有机功能化的硒化锡簇合物[(SnR(1))2SeCl4](1)、[(Snr(1))2Se2Cl2](2)、[(Snr(1))3Se4Cl](3)和[(Snr(1))4Se6](4),这取决于所用的溶剂和反应物的比例。核磁共振实验清楚地表明,通过随后的缩合步骤逐步形成1到4,伴随着ME3 SiCL的释放。此外,在酮-官能化的簇合物中加入肼可以生成[(Sn2(μ-R(3))(μ-Se)Cl4](5,R(3)=[CMe2CH2CME(NH)]2),[(SnR(2))3Se4Cl](6,R(2)=CMe2CH2C(NH2)Me),[(SnR(4)3Se4][SnCl3](7,R(4)=CMe2CH2C(NHPh)Me),[(SNR(2))4SE6](8)和[(SNR(4))4SE6](9)。用[Cu(PPh_3)_3Cl]和过量的(SiMe_3)_2Se处理4,生成[(R(1)Sn)_2Se_2(CuPPh_3)_2Se_2](10),这是文献报道的第一个离散型的锡/硒/铜簇合物。这些衍生化反应反映了有机锡硫化物化学与有机硒锡化合物化学的根本区别。
Reactions of R(1) SnCl3 (R(1) =CMe2 CH2 C(O)Me) with (SiMe3 )2 Se yield a series of organo-functionalized tin selenide clusters, [(SnR(1) )2 SeCl4 ] (1), [(SnR(1) )2 Se2 Cl2 ] (2), [(SnR(1) )3 Se4 Cl] (3), and [(SnR(1) )4 Se6 ] (4), depending on the solvent and ratio of the reactants used. NMR experiments clearly suggest a stepwise formation of 1 through 4 by subsequent condensation steps with the concomitant release of Me3 SiCl. Furthermore, addition of hydrazines to the keto-functionalized clusters leads to the formation of hydrazone derivatives, [(Sn2 (μ-R(3) )(μ-Se)Cl4 ] (5, R(3) =[CMe2 CH2 CMe(NH)]2 ), [(SnR(2) )3 Se4 Cl] (6, R(2) =CMe2 CH2 C(NNH2 )Me), [(SnR(4) )3 Se4 ][SnCl3 ] (7, R(4) =CMe2 CH2 C(NNHPh)Me), [(SnR(2) )4 Se6 ] (8), and [(SnR(4) )4 Se6 ] (9). Upon treatment of 4 with [Cu(PPh3 )3 Cl] and excess (SiMe3 )2 Se, the cluster fragments to form [(R(1) Sn)2 Se2 (CuPPh3 )2 Se2 ] (10), the first discrete Sn/Se/Cu cluster compound reported in the literature. The derivatization reactions indicate fundamental differences between organotin sulfide and organotin selenide chemistry.
DOI: 10.1002/chem.201403657
发表时间: 2014-10
期刊: Chemistry
影响因子: --
作者:
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发表时间: 2013-10-04
影响因子: 4.3
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DOI: 10.1002/zaac.201200155
发表时间: 2012
期刊: Zeitschrift für anorganische und allgemeine Chemie
影响因子: --
作者:
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