双（氨基酚酸酯）支持的pnictoranides：铋配合物中路易斯酸诱导的电聚合

IF 7.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science Pub Date : 2025-07-08 DOI:10.1039/d5sc03374h

Simon B. H. Karnbrock, Jan F. Köster, Isabelle Becker, Christopher Golz, Franc Meyer, Martí Gimferrer, Manuel Alcarazo

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引用次数: 0

摘要

报道了10-Pn-4双（氨基酚酸酯）负载的全系列pnictoranide阴离子的合成。这些阴离子与环戊二烯（II）二羰基片段[CpFe(CO)2]+配位，为P、As和Sb提供了相应的10-Pn-5配合物，而在Bi的情况下，发生了电子重分配，相应的12-Bi-5化合物被分离出来。通过x射线衍射分析、红外光谱、紫外-可见光谱和Mössbauer光谱，实验证实了刘易斯酸诱导电聚合的情况。铁配合物的有效氧化态分析使所有Pn的氧化态都为+3，而它预测铁原子在双导数中被还原为Fe(0)。Bi（6p）轨道与双（氨基酚酸酯）配体π系的混合以及该轨道向铁中心的有效电子给能解释这种情况。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Bis(amidophenolate)-supported pnictoranides: Lewis acid-induced electromerism in a bismuth complex

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Bis(amidophenolate)-supported pnictoranides: Lewis acid-induced electromerism in a bismuth complex

The synthesis of the complete series of 10-Pn-4 bis(amidophenolate)-supported pnictoranide anions is reported. Coordination of these anions to the cyclopentadienyliron(II) dicarbonyl fragment, [CpFe(CO)₂]⁺, delivers the corresponding 10-Pn-5 complexes for P, As and Sb, while in the case of Bi an electron redistribution takes place, and the corresponding 12-Bi-5 compound is isolated. This case of Lewis acid-induced electromerism has been experimentally confirmed through X-ray diffraction analyses as well as IR, UV-Vis and Mössbauer spectroscopy. Effective Oxidation State analysis of the Fe-complexes assigns an oxidation state +3 to all Pn, while it predicts the Fe-atom to be reduced to Fe(0) in the Bi-derivative. The mixture of the Bi(6p) orbital with the π-system of the bis(amidophenolate) ligand and the efficient electronic donation from this orbital to the Fe-center explain this situation.

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来源期刊

Chemical Science CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

14.40

自引率

4.80%

发文量

1352

审稿时长

2.1 months

期刊介绍： Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.