Reaction of 13‐Vertex Carboranes with Nucleophiles: Unprecedented Cage‐Carbon Extrusion and Formation of Monocarba‐<i>closo</i>‐dodecaborate Anions

Zhang, Jian; Chan, Hoi‐Shan; Xie, Zuowei

doi:10.1002/ange.200804249

Cited by 3 publications

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“…They showed some unique characteristics. For example, a 13-vertex closo -carborane accepted one electron to give a stable carborane radical anion with [2 n + 3] framework electrons 30 , 31 ; it also reacted with various nucleophiles to afford the cage carbon and/or cage boron extrusion products closo -CB 11 − , nido -CB 10 − , closo -CB 10 − , and closo -C 2 B 10 , depending on the nature of the nucleophiles 32 – 35 . Insertion of a metal fragment into a 14-vertex CAd nido -carborane was successful, resulting in the isolation and structural characterization of a 15-vertex metallacarborane 1,4-(CH 2 ) 3 -7-( p -cymene)-7,1,4-RuC 2 B 12 H 12 23 .…”

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confidence: 99%

Synthesis and X-ray characterization of 15- and 16-vertex closo-carboranes

et al. 2020

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Carboranes are a class of carbon-boron molecular clusters with three-dimensional aromaticity, and inherent robustness. These endowments enable carboranes as valuable building blocks for applications ranging from functional materials to pharmaceuticals. Thus, the chemistry of carboranes has received tremendous research interest, and significant progress has been made in the past decades. However, many attempts to the synthesis of carboranes with more than 14 vertices had been unsuccessful since the report of a 14-vertex carborane in 2005. The question arises as to whether these long sought-after molecules exist. We describe in this article the synthesis and structural characterization of 15- and 16-vertex closo-carboranes as well as 16-vertex ruthenacarborane. Such a success relies on the introduction of silyl groups to both cage carbons, stabilizing the corresponding nido-carborane dianions and promoting the capitation reaction with HBBr2·SMe2. This work would shed some light on the preparation of carboranes with 17 vertices or more, and open the door for studying supercarborane chemistry.

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confidence: 99%

Synthesis and X-ray characterization of 15- and 16-vertex closo-carboranes

et al. 2020

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“…[13] This 13-vertex carborane can also react with various nucleophiles to give cage-boron-or cage-carbon-extrusion products nido-CB 10 , closo-CB 10 , closo-CB 11 , or closo-C 2 B 10 , depending on the nature of the nucleophile. [14][15][16] When NaH was used as a nucleophile in the reaction with 1,2-(CH 2 ) 3 -1,2-C 2 B 11 H 11 , an unexpected a-deprotonation species, [1,2-CHA C H T U N G T R E N N U N G (CH 2 ) 2 -1,2-C 2 B 11 H 11 ] À , was obtained, which prompted us to study the deprotonation reaction of 13vertex carboranes with strong bases. Herein, we report the synthesis and structural characterization of 13-vertex carborane monoanions with exo C=C p bonding.…”

Section: Introductionmentioning

confidence: 99%

Reactions of 13‐Vertex Carboranes with Strong Bases: Synthesis and Structural Characterization of Carborane Monoanions with exo‐π Bonding

Zheng

Zhang

et al. 2013

Chemistry An Asian Journal

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Several monoanions of 13-vertex carboranes were prepared in high yields from the reactions of C,C'-linked 13-vertex carboranes with tBuOK or NaH in dry THF at room temperature. These monoanions were characterized by various spectroscopic methods, elemental analysis, and single-crystal X-ray diffraction. The results showed substantial double-bond character between the cage-carbon atom and the exo vicinal carbon atom, thus leading to charge delocalization into the cage. As a result, the atom-atom distances within the cage were elongated, with one broken C-B bond. However, the cage geometry of the monoanions remained very similar to that of their corresponding neutral 13-vertex closo-carboranes. These monoanions represent the first examples of 13-vertex carboranes with exo-π bonding to hypercarbon atoms.

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Recent Progress in the Chemistry of Supercarboranes

Zhang

Xie

2010

Chemistry An Asian Journal

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The chemistry of boron clusters has been dominated by icosahedral carboranes for over half a century. Only in recent years has significant progress been made in the chemistry of supercarboranes (carboranes with more than 12 vertices). A number of CAd (carbon-atoms-adjacent) 13- and 14-vertex carboranes, and CAp (carbon-atoms-apart) 13-vertex carboranes as well as their corresponding 14- and 15-vertex metallacarboranes have been successfully prepared and structurally characterized. This breakthrough relied on the use of CAd nido-carborane dianions as starting materials. These supercarboranes can undergo single-electron reduction to give stable supercarborane radical monoanions with [2n+3] framework electrons, and electrophilic substitution reaction to afford hexasubstituted supercarboranes. They can react with nucleophiles to offer monocarba-closo-dodecaborate monoanions from cage-carbon extrusion reactions. Their unique chemical properties make the chemistry of supercarboranes distinct from that of their 12-vertex analogues. These studies open up new possibilities for the development of polyhedral clusters of extraordinary size. This focus review offers an overview of recent advances in this growing research field.

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Reaction of 13‐Vertex Carboranes with Nucleophiles: Unprecedented Cage‐Carbon Extrusion and Formation of Monocarba‐closo‐dodecaborate Anions

Cited by 3 publications

References 29 publications

Synthesis and X-ray characterization of 15- and 16-vertex closo-carboranes

Synthesis and X-ray characterization of 15- and 16-vertex closo-carboranes

Reactions of 13‐Vertex Carboranes with Strong Bases: Synthesis and Structural Characterization of Carborane Monoanions with exo‐π Bonding

Recent Progress in the Chemistry of Supercarboranes

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