Theoretical Insight on the Formation Mechanism of a Trisubstituted Derivative of Closo-Decaborate Anion [B10H7O2CCH3(NCCH3)]0

被引：2
作者：
Klyukin, Ilya N. [1 ]
Kolbunova, Anastasia V. [1 ]
Novikov, Alexander S. [2 ,3 ,4 ]
Zhdanov, Andrey P. [1 ]
Zhizhin, Konstantin Yu. [1 ]
Kuznetsov, Nikolay T. [1 ]
机构：
[1] Russian Acad Sci, Kurnakov Inst Gen & Inorgan Chem, Leninskii Pr 31, Moscow 117907, Russia
[2] St Petersburg State Univ, Inst Chem, Univ Skaya Nab 7-9, St Petersburg 199034, Russia
[3] RUDN Univ, Peoples Friendship Univ Russia, Res Inst Chem, Miklukho Maklaya St 6, Moscow 117198, Russia
[4] ITMO Univ, Infochem Sci Ctr, Kronverksky Pr 49,Bldg A, St Petersburg 197101, Russia
来源：
INORGANICS | 2023年 / 11卷 / 05期
基金：
俄罗斯科学基金会;
关键词：
EINS; molecular mechanism; closo-borate anions; boron clusters; DFT; BASIS-SETS; NITRILIUM DERIVATIVES; DODECABORATE ANION; CHEMISTRY; BORANES; BORON; FUNCTIONALIZATION; SUBSTITUTION; HALOGENATION; VALENCE;
D O I：
10.3390/inorganics11050201
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
A theoretical modelling of the interaction process between a protonated complex of carboxonium derivative [2,6-B10H8O2CCH3*H-fac](0) and acetonitrile molecule CH3CN was carried out. As a result of the process, a trisubstituted [B10H7O2CCH3(NCCH3)](0) derivative was formed. This reaction has an electrophile-induced nucleophilic substitution (EINS) mechanism. The main intermediates and transition states of the substitution process were established. As in the case of all previously investigated EINS processes, the key intermediate was an anion with a dihydrogen H-2 fragment attached to one boron atom (B(H-2) structure motif). The process of nucleophilic substitution can proceed on a different position of the cluster cage. The main potential pathways were assessed. It was established that substitution on the B-4 position of the cluster cage was the most energetically favourable, and the [2,4,6-B10H7O2CCH3(NCCH3)](0) isomer was formed.
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页数：14
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