Insertion of Carbenes into Deprotonated nido-Undecaborane, B11H132–

Jacek Pecyna; Igor Rončević; Josef Michl

doi:10.3390/molecules24203779

Insertion of Carbenes into Deprotonated nido-Undecaborane, B₁₁H₁₃^2–

Jacek Pecyna, Igor Rončević, Josef Michl

Computational and Theoretical Chemistry

The Regents of The University of Colorado

Research output: Contribution to journal › Article › peer-review

Abstract

We have examined the insertion of carbenes carrying leaving groups into the [nido-B₁₁H₁₃]²⁻ dianion to form the [closo-1-CB₁₁H₁₂]⁻ anion. The best procedure uses CF₃SiMe₃ and LiCl as the source of CF₂. It is simple, convenient and scalable and proceeds with 70–90% yield. Density functional calculations have been used to develop a mechanistic proposal that accounts for the different behavior of CF₂, requiring only one equivalent of base for successful conversion of Na[nido-B₁₁H₁₄]⁻ to [closo-1-CB₁₁H₁₂]⁻, and CCl₂ and CBr₂, which require more.

Original language	English
Article number	3779
Pages (from-to)	1-13
Number of pages	13
Journal	Molecules
Volume	24
Issue number	20
DOIs	https://doi.org/10.3390/molecules24203779
Publication status	Published - 21 Oct 2019

Keywords

carboranes
[closo-1-CB11H12]− anion
difluorocarbene

Access to Document

10.3390/molecules24203779

Cite this

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title = "Insertion of Carbenes into Deprotonated nido-Undecaborane, B11H132–",

abstract = "We have examined the insertion of carbenes carrying leaving groups into the [nido-B11H13]2− dianion to form the [closo-1-CB11H12]− anion. The best procedure uses CF3SiMe3 and LiCl as the source of CF2. It is simple, convenient and scalable and proceeds with 70–90% yield. Density functional calculations have been used to develop a mechanistic proposal that accounts for the different behavior of CF2, requiring only one equivalent of base for successful conversion of Na[nido-B11H14]− to [closo-1-CB11H12]−, and CCl2 and CBr2, which require more.",

keywords = "carboranes, [closo-1-CB11H12]− anion, difluorocarbene",

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AU - Rončević, Igor

AU - Michl, Josef

PY - 2019/10/21

Y1 - 2019/10/21

N2 - We have examined the insertion of carbenes carrying leaving groups into the [nido-B11H13]2− dianion to form the [closo-1-CB11H12]− anion. The best procedure uses CF3SiMe3 and LiCl as the source of CF2. It is simple, convenient and scalable and proceeds with 70–90% yield. Density functional calculations have been used to develop a mechanistic proposal that accounts for the different behavior of CF2, requiring only one equivalent of base for successful conversion of Na[nido-B11H14]− to [closo-1-CB11H12]−, and CCl2 and CBr2, which require more.

AB - We have examined the insertion of carbenes carrying leaving groups into the [nido-B11H13]2− dianion to form the [closo-1-CB11H12]− anion. The best procedure uses CF3SiMe3 and LiCl as the source of CF2. It is simple, convenient and scalable and proceeds with 70–90% yield. Density functional calculations have been used to develop a mechanistic proposal that accounts for the different behavior of CF2, requiring only one equivalent of base for successful conversion of Na[nido-B11H14]− to [closo-1-CB11H12]−, and CCl2 and CBr2, which require more.

KW - carboranes

KW - [closo-1-CB11H12]− anion

KW - difluorocarbene

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