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有机锑（V）氮族元素键供体对阴离子结合位点的空间选择：一项实验与计算研究

Steric Selection of Anion Binding Sites by Organoantimony(V) Pnictogen Bond Donors: An Experimental and Computational Study.

作者信息

Murphy Brendan L, Maltz Logan T, Gabbaï François P

机构信息

Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255, United States.

出版信息

Inorg Chem. 2024 Dec 16;63(50):23568-23576. doi: 10.1021/acs.inorgchem.4c03178. Epub 2024 Dec 3.

DOI:10.1021/acs.inorgchem.4c03178
PMID:39626108
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11653240/
Abstract

Catecholatostiboranes have emerged as useful Lewis acids in several applications. To better understand the factors that control the properties of these species, we examined the Lewis acidities of (-CClO)Sb(-Tol) (, Tol = tolyl) and (-CClO)Sb(-Tol) (), two triarylcatecholatostiboranes that differ by the nature of the aryl substituent. Fluoride anion binding studies indicate that is more Lewis acidic than , a factor readily assigned to the steric crowding around antimony in the case of the -tolyl derivative. But, while binds F trans to a Sb-C bond as is typical of catecholatostiboranes, prefers binding trans to a Sb-O bond. Computational analyses of and reveal the existence of several σ holes, and an activation strain analysis is employed to elucidate the origin of these stiboranes' anion-binding geometry preferences.

摘要

儿茶酚硼酸酯在多种应用中已成为有用的路易斯酸。为了更好地理解控制这些物种性质的因素，我们研究了(-CClO)Sb(-Tol)（，Tol = 甲苯基）和(-CClO)Sb(-Tol)（）这两种三芳基儿茶酚硼酸酯的路易斯酸度，它们因芳基取代基的性质不同而有所差异。氟阴离子结合研究表明，比更具路易斯酸性，这一因素很容易归因于 -甲苯基衍生物中锑周围的空间拥挤。但是，虽然像儿茶酚硼酸酯通常那样与F以反式结合到一个Sb-C键上，但更喜欢与反式结合到一个Sb-O键上。对和的计算分析揭示了几个σ 空穴的存在，并采用活化应变分析来阐明这些硼酸酯阴离子结合几何偏好的起源。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6c3/11653240/cb1ea2ea4439/ic4c03178_0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6c3/11653240/eea8358b9bea/ic4c03178_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6c3/11653240/4eeef08627af/ic4c03178_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6c3/11653240/f901df56c1bc/ic4c03178_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6c3/11653240/b75c51992b09/ic4c03178_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6c3/11653240/4905cf12a339/ic4c03178_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6c3/11653240/7022340143ba/ic4c03178_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6c3/11653240/588d50bead44/ic4c03178_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6c3/11653240/8f4edd4ade46/ic4c03178_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6c3/11653240/cb1ea2ea4439/ic4c03178_0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6c3/11653240/eea8358b9bea/ic4c03178_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6c3/11653240/4eeef08627af/ic4c03178_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6c3/11653240/f901df56c1bc/ic4c03178_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6c3/11653240/b75c51992b09/ic4c03178_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6c3/11653240/4905cf12a339/ic4c03178_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6c3/11653240/7022340143ba/ic4c03178_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6c3/11653240/588d50bead44/ic4c03178_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6c3/11653240/8f4edd4ade46/ic4c03178_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6c3/11653240/cb1ea2ea4439/ic4c03178_0009.jpg

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Tunable Pnictogen Bonding at the Service of Hydroxide Transport across Phospholipid Bilayers.用于跨磷脂双分子层传输氢氧根离子的可调谐氮族元素键合
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