Preparation of [closo-CB11H12]- by dichlorocarbene insertion into [nido-B11H14]-

被引：74

作者：

Franken, A ^{[1
]}

King, BT ^{[1
]}

Rudolph, J ^{[1
]}

Rao, P ^{[1
]}

Noll, BC ^{[1
]}

Michl, J ^{[1
]}

机构：

[1] Univ Colorado, Dept Chem & Biochem, Boulder, CO 80309 USA

来源：

COLLECTION OF CZECHOSLOVAK CHEMICAL COMMUNICATIONS | 2001年 / 66卷 / 08期

关键词：

boranes; carboranes; closo-CB11H12](-) anion; dihalocarbenes; haloforms;

D O I：

10.1135/cccc20011238

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

In strongly basic media, the [nido-B11H14](-) anion reacts with the haloforms. Dehydrogenation to [closo-B11H11](2-) is the only reaction observed with iodoform. With chloroform and bromoform, the cage is expanded by dihalocarbene insertion. The dominant products are the [closo-CB11H12](-) and the [2-Br-closo-CB11H12](-) anion, respectively. The chief side product is the [closo-B11H11](2-) anion, which results from dehydrogenation of the starting material. It was identified by B-11 NMR spectroscopy and isolated after acidic aqueous workup in the form of the [nido-7-OH-B11H13](-) anion. Since the starting [nido-B11H14] anion is available from NaBH4 and BF3. Et2O in 50% yield, its conversion to [closo-CB11H12](-) with chloroform and base in a 40% yield represents a useful laboratory route to the numerous known but previously very expensive derivatives of [closo-CB11H12](-), highly prized for their very low nucleophilicity.

引用

页码：1238 / 1249

页数：12

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