Sulfinylamine metathesis at oxo metal species--convenient entry into imido metal chemistry.
Sulfinylamine metathesis at oxo metal species--convenient entry into imido metal chemistry.
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氧代金属物种的亚磺胺复分解——方便进入亚氨基金属化学。
DOI：
10.1039/c0dt01133a
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发表时间：
2011
影响因子：
4
通讯作者：
J. Sundermeyer
中科院分区：
文献类型：
--
作者：
K. Rufanov;Jennifer Kipke;J. Sundermeyer
描述了通过与弯曲的、因此非常反应性的亚磺酰胺R-NSO和亚磺酰基磺酰胺R-SO（2）-NSO的复分解，末端金属氧代官能团被N-有机和N-磺酰亚胺官能团交换。它表明，在许多情况下，亚磺酰胺复分解提供了一个更方便的进入亚氨基复合物的合成比更好地研究异氰酸酯复分解在氧代配合物或缩合反应与胺和甲硅烷基化胺。改进了一些已知的关键化合物的合成方法，并合成了几种新的[V（NR）Cl（3）]和[M（NR）（2）Cl（2）]（M = Cr，Mo，W）配合物。重点介绍了具有吸电子N-取代基的无碱刘易斯酸的合成。令人惊讶的是，甚至[CrO（2）Cl（2）]也被亚磺酰胺选择性地转化为芳基亚氨基衍生物，而没有被二氧化硫还原。本文报道了新型卤代芳基亚胺配合物[Cr（NAr）（2）Cl（2）] Ar = C（6）F（5）和2，4，6-Cl（3）C（6）H（2）的X射线晶体学测定结果。
The exchange of terminal metal oxo functionalities by N-organo and N-sulfonylimido functionalities via metathesis with bent, thus very reactive sulfinyl amines R-NSO and sulfinyl sulfonylamides R-SO(2)-NSO is described. It is demonstrated that in many cases sulfinyl amine metathesis offers a more convenient entry into imido complex synthesis than the much better investigated isocyanate metathesis at oxo complexes or condensation reactions with amines and silylated amines. Improved syntheses for some known key compounds and several new complexes of the type [V(NR)Cl(3)] and [M(NR)(2)Cl(2)] (M = Cr, Mo, W) are described. Emphasis is put on the synthesis of formerly unknown base free Lewis acids with electron-withdrawing N-substituents such as haloaryl and sulfonylaryl. Surprisingly, even [CrO(2)Cl(2)] is selectively transformed by sulfinylamines into aryl imido derivatives without any reduction by sulfur dioxide. The molecular structures of novel haloaryl imido complexes [Cr(NAr)(2)Cl(2)] Ar = C(6)F(5) and 2,4,6-Cl(3)C(6)H(2) as determined by X-ray crystallography are reported.