Isolation of a phosphinidene sulfide and selenide

IF 7.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science Pub Date : 2025-07-10 DOI:10.1039/d5sc04352b

Chenyang Hu, Maren Pink, Jose M. Goicoechea

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Abstract

We describe the synthesis of an isolable phosphinidene sulfide and phosphinidene selenide (BnArNP Abstract Image

Ch; Ch = S, Se) by reaction of a sterically protected phosphinidene oxide (BnArNP Abstract Image

O) with Lawesson's or Woollins' reagents, respectively. These compounds reveal short P Abstract Image

E bonds consistent with a high degree of p_π–p_π double bond character. The pendant amido group on the phosphorus atom plays an important role in their stabilization through nitrogen lone pair donation into the P–Ch π* orbital, and evidence for isomerism about the N–P bond was observed for both species. Dimeric intermediates featuring mixed phosphorus(III)/phosphorus(V) centers could be isolated and structurally authenticated during the course of these studies providing some insight into the mechanism of formation of the titular compounds.

Abstract Image

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硫化物和硒化物的分离

合成了一种可分离的硫化磷和硒化磷（BnArNPCh）；Ch = S, Se)分别与Lawesson试剂和Woollins试剂进行了立体保护的氧化膦（BnArNPO）反应。这些化合物的PE键较短，具有高度的ppπ - ppπ双键特征。磷原子上的垂坠胺基通过氮孤对给予P-Ch π*轨道，在稳定磷原子方面起着重要作用，并且在两种物质中都观察到N-P键的异构现象。在这些研究过程中，具有混合磷(III)/磷(V)中心的二聚体中间体可以被分离出来并进行结构鉴定，从而对名义化合物的形成机制提供了一些见解。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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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.