Regioselective 1,1′,3,3′-tetrazincation [C–H to C–Zn(tBu)] of ferrocene has been achieved by reaction of a fourfold excess of di-t-butylzinc (tBu₂Zn) with sodium 2,2,6,6-tetramethylpiperidide (NaTMP) in hexane solution manifested in the trimetallic iron–sodium–zinc complex [Na₄(TMP)₄Zn₄(tBu)₄{(C₅H₃)₂Fe}], 1. X-ray crystallographic studies supported by DFT modelling reveal the structure to be an open inverse crown in which two [Na(TMP)Zn(tBu)Na(TMP)Zn(tBu)]²⁺ cationic units surround a {(C₅H₃)₂Fe}⁴⁻ tetraanion. Detailed C₆D₆ NMR studies have assigned the plethora of ¹H and ¹³C chemical shifts of this complex. It exists in a major form in which capping and bridging TMP groups interchange, as well as a minor form that appears to be an intermediate in this complicated exchange phenomenon. Investigation of 1 has uncovered two distinct reactivities. Two of its peripheral t-butyl carbanions formally deprotonate toluene at the lateral methyl group to generate benzyl ligands that replace these carbanions in [Na₄(TMP)₄Zn₄(tBu)₂(CH₂Ph)₂{(C₅H₃)₂Fe}], 2, which retains its tetrazincated ferrocenyl core. Benzyl-Na π-arene interactions are a notable feature of 2. In contrast, reaction with pyridine affords the crystalline product {[Na·4py][Zn(py*)₂(tBu)·py]}_∞, 3, where py is neutral pyridine (C₅H₅N) and py* is the anion (4-C₅H₄N), a rare example of pyridine deprotonated/metallated at the 4-position. This ferrocene-free complex appears to be a product of core reactivity in that the core-positioned ferrocenyl anions of 1, in company with TMP anions, have formally deprotonated the heterocycle.

中文翻译：

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区域选择性的1,1'，3,3'-四锌二茂铁配合物，显示核心和外围反应性

区域选择性1,1'，3,3'- tetrazincation [C-H至C-Zn系（吨丁基）]二茂铁的已经由四倍过量的反应来实现二吨-butylzinc（吨卜₂ Zn）的钠三金属铁-钠-锌络合物[Na ₄（TMP）₄ Zn ₄（t Bu）₄ {（C ₅ H ₃）₂ Fe}]中显示的2,2,6,6-四甲基哌啶（NaTMP）在己烷溶液中的存在，1。DFT建模支持的X射线晶体学研究表明，该结构是一个开放的反向冠，其中两个[Na（TMP）Zn（t Bu）Na（TMP）Zn（tBu）] ²⁺阳离子单元围绕{（C ₅ H ₃）₂ Fe} ^4-四阴离子。详细的C ₆ D ₆ NMR研究确定了该配合物的¹ H和¹³ C化学位移过多。它以封顶和桥接TMP组互换的主要形式存在，而次要形式似乎是这种复杂交换现象的中间形式。对1的调查发现了两个不同的反应性。它的两个周边叔丁基碳负离子在甲基侧基上使甲苯去质子化，生成取代[Na]中这些碳负离子的苄基配体。₄（TMP） ₄ Zn ₄（ t Bu） ₂（CH ₂ Ph） ₂ {（C ₅ H ₃） ₂ Fe}]， 2保留其四锌二茂铁基核心。苄基-Naπ-芳烃相互作用是2的显着特征。相反，与吡啶反应得到结晶产物{[Na·4py] [Zn（py *） ₂（ t Bu）·py]} _∞， 3，其中py是中性吡啶（C ₅ H ₅ N）和py *是阴离子（4-C ₅ H ₄N），吡啶在4位上去质子化/金属化的罕见例子。该不含二茂铁的配合物似乎是核心反应性的产物，因为与TMP阴离子结合的位于核心的1的二茂铁阴离子与形式上的杂环质子化。