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单体CpAl(i)：合成、反应性及价异构概念

Monomeric CpAl(i): synthesis, reactivity, and the concept of valence isomerism.

作者信息

Hofmann Alexander, Tröster Tobias, Kupfer Thomas, Braunschweig Holger

机构信息

Institut für Anorganische Chemie , Julius-Maximilians-Universität Würzburg , Am Hubland , 97074 Würzburg , Germany . Email:

Institute for Sustainable Chemistry & Catalysis with Boron , Julius-Maximilians-Universität Würzburg , Am Hubland , 97074 Würzburg , Germany.

出版信息

Chem Sci. 2019 Jan 14;10(11):3421-3428. doi: 10.1039/c8sc05175e. eCollection 2019 Mar 21.

DOI:10.1039/c8sc05175e
PMID:30996931
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6429597/
Abstract

With the isolation of CpAl (), the first monomeric Cp-based Al(i) species could be realized in a pure form a three-step reaction sequence (salt elimination/adduct formation/adduct cleavage) starting from readily available AlBr. Due to its monomeric structure, reactions involving were found to proceed more selectively, faster, and under milder conditions than for tetrameric (Cp*Al). Thus, readily formed simple Lewis acid-base adducts with BuAlCl () and AlBr (), reactions that before have always been interfered with by the presence of aluminum halide bonds. In addition, the 2 : 1 reaction of with AlBr enabled the realization of the very rare trialuminum adduct species . also reacted rapidly with NO and PhN at room temperature to afford AlO and AlN heterocycles and , respectively. With the structural characterization of products and , the reaction of monovalent with CpAlBr () provided the first experimental evidence for the concept of valence isomerism between dialanes and their Al(i)/Al(iii) Lewis adducts.

摘要

随着CpAl（）的分离，第一种单体形式的基于Cp的Al（i）物种能够以纯形式通过一个三步反应序列（盐消除/加合物形成/加合物裂解）从容易获得的AlBr实现。由于其单体结构，发现涉及的反应比四聚体（Cp*Al）的反应更具选择性、更快且在更温和的条件下进行。因此，很容易与BuAlCl（）和AlBr（）形成简单的路易斯酸碱加合物，而以前这些反应总是受到卤化铝键的存在的干扰。此外，与AlBr的2∶1反应使得非常罕见的三铝加合物物种得以实现。在室温下也能与NO和PhN迅速反应，分别生成AlO和AlN杂环化合物和。随着产物和的结构表征，一价与CpAlBr（）的反应为二铝烷及其Al（i）/Al（iii）路易斯加合物之间的价异构概念提供了首个实验证据。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0fb1/6429597/fa78a51f5880/c8sc05175e-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0fb1/6429597/f133ff3c1a7a/c8sc05175e-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0fb1/6429597/5c5ad4680c5e/c8sc05175e-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0fb1/6429597/0b64158aeb5c/c8sc05175e-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0fb1/6429597/1500d033862c/c8sc05175e-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0fb1/6429597/b7cdd1692166/c8sc05175e-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0fb1/6429597/0e0864c85b39/c8sc05175e-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0fb1/6429597/298d0e7a8fb5/c8sc05175e-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0fb1/6429597/482153afff29/c8sc05175e-s4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0fb1/6429597/ac702f47f537/c8sc05175e-s5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0fb1/6429597/fa78a51f5880/c8sc05175e-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0fb1/6429597/f133ff3c1a7a/c8sc05175e-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0fb1/6429597/5c5ad4680c5e/c8sc05175e-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0fb1/6429597/0b64158aeb5c/c8sc05175e-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0fb1/6429597/1500d033862c/c8sc05175e-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0fb1/6429597/b7cdd1692166/c8sc05175e-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0fb1/6429597/0e0864c85b39/c8sc05175e-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0fb1/6429597/298d0e7a8fb5/c8sc05175e-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0fb1/6429597/482153afff29/c8sc05175e-s4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0fb1/6429597/ac702f47f537/c8sc05175e-s5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0fb1/6429597/fa78a51f5880/c8sc05175e-f5.jpg

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