Synthesis and properties of new ditertiary stibines based upon o-, m- or p-xylyl and m- or p-phenylene backbones and their complexes with tungsten, iron and nickel carbonyls.
Synthesis and properties of new ditertiary stibines based upon o-, m- or p-xylyl and m- or p-phenylene backbones and their complexes with tungsten, iron and nickel carbonyls.
复制标题
基于邻、间或对二甲苯基和间或对亚苯基骨架及其与钨、铁和镍羰基的络合物的新型二叔锑的合成和性能。
DOI：
10.1039/b312083j
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发表时间：
2004
影响因子：
4
通讯作者：
M. Webster
中科院分区：
文献类型：
--
作者：
W. Levason;M. Matthews;G. Reid;M. Webster
从 Me2SbCl（方便地由 Me2PhSb 和 HCl 气体原位制备）高产率合成 1,2-、1,3- 和 1,4-二甲苯基二替宾（分别为 1,2-C6H4(CH2SbMe2)2、1,3-C6H4(CH2SbMe2)2、1,4-C6H4(CH2SbMe2)2）并报告了适当的二格氏试剂。类似地制备1,3-和1,4-亚苯基二替宾、1,3-C6H4(SbMe2)2 和1,4-C6H4(SbMe2)2。新配体已通过质谱、 1H 和 13C[1H] NMR 光谱以及甲硫代衍生物的制备进行了表征。 1,4-C6H4(CH2SbMe2)2 和[1,3-C6H4(CH2SbMe3)2]I2 的晶体结构已确定。 1,2-C6H4(CH2SbPh2)2 的合成也以中等收率实现，并且 distibine 转化为四碘衍生物 1,2-C6H4(CH2SbPh2I2)2。通过镍、铁和羰基钨配合物的合成和表征，探讨了这些配体可用的配位模式。 [[Fe(CO)4]2[micro-1,3-C6H4(CH2SbMe2)2]]的晶体结构已确定。这些羰基衍生物的光谱性质与其他锑配体的配合物进行了比较，在某些情况下与二膦和二胂配合物进行了比较，以探测新配体的电子性质。
High yield syntheses for 1,2-, 1,3-, and 1,4-xylyl distibines (1,2-C6H4(CH2SbMe2)2, 1,3-C6H4(CH2SbMe2)2, 1,4-C6H4(CH2SbMe2)2, respectively) from Me2SbCl (conveniently made in situ from Me2PhSb and HClgas) and the appropriate di-Grignard are reported. The 1,3- and 1,4-phenylene distibines, 1,3-C6H4(SbMe2)2 and 1,4-C6H4(SbMe2)2, were made similarly. The new ligands have been characterised by mass spectrometry, 1H and 13C[1H] NMR spectroscopy, and by the preparation of methiodide derivatives. The crystal structures of 1,4-C6H4(CH2SbMe2)2 and [1,3-C6H4(CH2SbMe3)2]I2 have been determined. The synthesis of 1,2-C6H4(CH2SbPh2)2 has been achieved similarly in modest yield and the distibine converted into the tetra-iodo-derivative 1,2-C6H4(CH2SbPh2I2)2. The coordination modes available to these ligands have been probed by the synthesis and characterisation of complexes with nickel, iron and tungsten carbonyls. The crystal structure of [[Fe(CO)4]2[micro-1,3-C6H4(CH2SbMe2)2]] has been determined. The spectroscopic properties of these carbonyl derivatives have been compared with those of complexes of other antimony ligands, and in some cases with diphosphine and diarsine complexes, to probe the electronic properties of the new ligands.