Tetrahedral versus planar four-coordinate carbon: a sulfonyl-substituted methandiide.
Tetrahedral versus planar four-coordinate carbon: a sulfonyl-substituted methandiide.
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四面体与平面四配位碳：磺酰基取代的甲烷二化物
DOI：
10.1002/chem.201201369
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发表时间：
2012
期刊：
影响因子：
--
通讯作者：
V. H. Gessner
中科院分区：
文献类型：
--
作者：
P. Schröter;V. H. Gessner
近几十年来，主族元素化合物在不寻常的氧化态或配位环境中的电子结构激发了人们的研究。第二排元素和它们的重同系物之间的差异已经用许多例子来说明，例如，人们深入研究的烯烃和炔烃与它们的重反式类似物之间的差异。[1]虽然碳的化学属于化学中最古老和研究最多的领域，但新的成键模式和概念仍在建立中。最近的一些例子是在双原子C2中引入四键[2]或在碳二磷烷(碳)中引入二价碳(0)。[3]这项研究通常是由这些化合物独特的反应性驱动的，这是基于不寻常的电子结构。因此，键活化反应，一个长期局限于过渡金属络合物的研究领域，已经开始发展。[4]碳化合物化学中一个长期无争议的概念是四配位碳的四面体排列，如范特霍夫S的建议所示。[5]然而，这一规则受到了挑战，首先，Schleyer和他的同事通过计算预测了平面四配位碳的电正取代基稳定性。[6]最后，这一预测在2010年得到了利德尔和他的同事的实验验证。[7，8]然而，没有其他已知的甲烷化合物，如II，尽管数量有限，但还没有被证明具有这种平面碳构象的化合物。[9，10，11]这引发了一个问题，即平坦化是仅仅是配位侧臂引起的几何限制的结果，还是来自未知的碳的成键基序。为了解决这个问题，我们着手制备新的二硫代甲烷。由于它们的可及性非常有限，到目前为止，研究集中在但不限于容易获得的双(膦)取代化合物。[12]为了阐明分子内施主功能对锂配位的影响，必须检查双金属碳上的进一步取代基。[13]在这里，我们描述了磺酰取代的双阴离子的合成和结构，并讨论了它的电子结构与四配位碳原子的平面化。
The electronic structure of compounds with main-group elements in unusual oxidation states or coordination environments has inspired research during recent decades. Differences between the second-row elements and their heavier congeners have been illustrated with many examples, such as the intensively studied differences between alkenes and alkynes compared with their heavier trans-bent analogues.[1] Although the chemistry of carbon belongs to the oldest and most studied fields in chemistry, new bonding modes and concepts are still being established. Some recent examples are the introduction of quadruple bonding in diatomic C2[2] or divalent carbon (0) in carbodiphosphoranes (carbones).[3] This research is often driven by the unique reactivity of these compounds, which is based on the unusual electronic structure. As such, bond activation reactions, a research field long limited to transition-metal complexes, has started to evolve.[4] One of the long indisputable concepts in the chemistry of carbon compounds is that of the tetrahedral arrangement of fourcoordinate carbon, as manifested in van t Hoff s proposal.[5] However, this rule has been challenged, firstly, by computation by Schleyer and co-workers predicting the stabilization of planar tetracoordinate carbon by electropositive substituents.[6] Finally, this prediction was verified experimentally in 2010 by Liddle and co-workers, who succeeded in the isolation of a compound with such a planar four-coordinate carbon in the bis (phosphonium)-stabilized methandiide I.[7, 8] However, no other known methandiide, such as II, although limited in number, has been shown to feature this planar carbon conformation.[9, 10, 11] This provokes the question, of whether planarization is solely the result of geometric restrictions caused by the coordinating side arms or whether it results from an unknown bonding motif of carbon. To address this question, we set out to prepare new dilithio methandiides. Due to their extremely limited accessibility, investigations have so far concentrated on, but are not limited to, the readily available bis (phosphonium)-substituted compounds.[12] To clarify the influence of the Li coordination by intramolecular donor functions, further substituents at the dimetallated carbon have to be examined.[13] Herein, we describe the synthesis and structure of a sulfonyl-substituted geminal dianion and discuss its electronic structure with respect to the planarization of the four-coordinate carbon atom.
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