Christian Klein-Hessling, Tobias Blockhaus, Karlheinz Sünkel
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引用次数: 0
摘要
从[Mn(C5H4Br)(PPh3)(CO)2]（1a）开始，得到了环戊基硫醚[Mn(C5H4SMe)(PPh3)(CO)2]（1b）和[Mn{C5H4-nBr(SMe)n}(PPh3)(CO)2]（化合物 2 的 n = 1，化合物 3 的 n = 2，化合物 4 的 n = 3）、以正丁基锂（n-BuLi）、二异丙基酰胺锂（LDA）或四甲基哌啶锂（LiTMP）为碱，然后用 MeSSMe 进行亲电淬火。将[Mn(C5Br5)(PPh3)(CO)2]与 n-BuLi 和 MeSSMe 逐步连续反应，最终得到[Mn{C5(SMe)5}(PPh3)(CO)2]（11），这是迄今为止报道的第五个含有过硫化环戊二烯环的复合物。我们确定了 1b、3、4 和 11 的分子和晶体结构，并研究了 S...S 和 S...Br 的相互作用。结果表明，虽然存在一些此类相互作用，但它们对晶体中分子的排列并不重要。
Synthesis, spectroscopic and crystallographic characterization of various cymantrenyl thioethers [Mn{C5HxBry(SMe)z}(PPh3)(CO)2].
Starting from [Mn(C5H4Br)(PPh3)(CO)2] (1a), the cymantrenyl thioethers [Mn(C5H4SMe)(PPh3)(CO)2] (1b) and [Mn{C5H4-nBr(SMe)n}(PPh3)(CO)2] (n = 1 for compound 2, n = 2 for 3 and n = 3 for 4) were obtained, using either n-butyllithium (n-BuLi), lithium diisopropylamide (LDA) or lithium tetramethylpiperidide (LiTMP) as base, followed by electrophilic quenching with MeSSMe. Stepwise consecutive reaction of [Mn(C5Br5)(PPh3)(CO)2] with n-BuLi and MeSSMe led finally to [Mn{C5(SMe)5}(PPh3)(CO)2] (11), only the fifth complex to be reported containing a perthiolated cyclopentadienyl ring. The molecular and crystal structures of 1b, 3, 4 and 11 were determined and were studied for the occurrence of S...S and S...Br interactions. It turned out that although some interactions of this type occurred, they were of minor importance for the arrangement of the molecules in the crystal.
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Acta Crystallographica Section C: Structural Chemistry is continuing its transition to a journal that publishes exciting science with structural content, in particular, important results relating to the chemical sciences. Section C is the journal of choice for the rapid publication of articles that highlight interesting research facilitated by the determination, calculation or analysis of structures of any type, other than macromolecular structures. Articles that emphasize the science and the outcomes that were enabled by the study are particularly welcomed. Authors are encouraged to include mainstream science in their papers, thereby producing manuscripts that are substantial scientific well-rounded contributions that appeal to a broad community of readers and increase the profile of the authors.
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