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较重的二茂铁基nictogenium离子。

Heavier Diferrocenylpnictogenium Ions.

作者信息

Stoian Corina, Olaru Marian, Demeshko Serhiy, Fischer Malte, Mebs Stefan, Hupf Emanuel, Beckmann Jens

机构信息

Institut für Anorganische Chemie und Kristallographie, Universität Bremen, Leobener Straße 7, 28359, Bremen, Germany.

Institut für Anorganische Chemie, Georg-August-Universität Göttingen, Tammannstraße 4, 37077, Göttingen, Germany.

出版信息

Chemistry. 2025 Jan 2;31(1):e202403555. doi: 10.1002/chem.202403555. Epub 2024 Nov 27.

DOI:10.1002/chem.202403555
PMID:39471106
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11711300/
Abstract

The synthesis, characterization and reactivity of the diferrocenylphosphenium ion [FcP] was extended to the heavier diferrocenylpnictogenium ions, [FcE] (E=As, Sb, Bi). The lighter diferrocenylnitrenium ion, [FcN], was detected by mass spectrometry, but could not be isolated. The molecular structures of [FcE] (E=P, As, Sb, Bi) reveal intramolecular coordination of the iron atoms, which counterbalance the electron deficiency of the pnictogens without affecting the strong Lewis acidities, which were determined according to the method of Gutmann and Beckett. The (electro-)chemical oxidation and reduction afforded the dications [FcE] (E=P (unstable), As) and the neutral dipnictogens FcEEFc (E=P, As).

摘要

二茂铁基磷鎓离子[FcP]的合成、表征及反应活性扩展至更重的二茂铁基氮族元素鎓离子[FcE]（E = As、Sb、Bi）。较轻的二茂铁基亚胺鎓离子[FcN]通过质谱检测到，但无法分离出来。[FcE]（E = P、As、Sb、Bi）的分子结构揭示了铁原子的分子内配位，这种配位在不影响根据古特曼和贝克特方法测定的强路易斯酸度的情况下，抵消了氮族元素的电子不足。（电）化学氧化和还原得到了双阳离子[FcE]（E = P（不稳定）、As）和中性双氮族元素FcEEFc（E = P、As）。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b788/11711300/8bd4df9a4e6b/CHEM-31-e202403555-g012.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b788/11711300/effad2a9f689/CHEM-31-e202403555-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b788/11711300/305b9231b8c4/CHEM-31-e202403555-g013.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b788/11711300/784c79dfa16d/CHEM-31-e202403555-g009.jpg
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