Functionalisation of the nido-dicarbaborate anion nido-7,8-C2B9H12- by hydride abstraction

被引：22
|
作者：
Frank, Rene [1 ]
Auer, Henry [1 ]
Hey-Hawkins, Evamarie [1 ]
机构：
[1] Univ Leipzig, Inst Anorgan Chem, D-04103 Leipzig, Germany
来源：
JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2013年 / 747卷
关键词：
nido-7,8-C2B9H12-; Water-free hydride abstraction; Symmetric EINS-type reaction; Asymmetric electrophilic substitution; Charge compensation; MOLECULAR-STRUCTURE; CRYSTAL-STRUCTURES; DERIVATIVES; ION; DODECAHYDRO-7,8-DICARBA-NIDO-UNDECABORATE; HALOGENATION; ALKYLATION; TRANSITION; CARBORANES; COMPLEXES;
D O I：
10.1016/j.jorganchem.2013.04.031
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
Substitution at the dicarbaborate anion nido-7,8-C2B9H12- (1) with precise hydride abstraction leads to symmetric products 10-R-nido-7,8-C2B9H11, e.g., 10-[cyclo-(CH2)(4)O]-nido-7,8-C2B9H11 (2) and 10-[ cyclo( CH2)(4)S]-nido-7,8-C2B9H11 (3). However, this approach has been limited to acetaldehyde as hydride acceptor in an acidified, aqueous two-phase system. In expanding the concept of hydride abstraction, we have found that acetone, activated by AlCl3, is capable of accepting hydride with substitution of the symmetric B10 position in the presence of suitable donor molecules (Lewis bases). Thus, by employing a one-phase water-free system, 2 and 3 as well as moisture-sensitive 10-CH3CN-nido-7, 8-C2B9H11 (4) were obtained in good to high yield. Reactions with 1 in neat acetone gave 10-HO-nido-7, 8-C2B9H11- (7). An alternative reagent for hydride abstraction in 1 is tritylium tetrafluoroborate (Ph3CBF4), which gave 10-Ph2S-nido-7, 8-C2B9H11 (11) in the presence of Ph2S. The Ph2S moiety in 11 could easily be replaced by pyridine and triethylamine, giving 10-C5H5N-nido-7,8-C2B9H11 (12) and 10- Et3N-nido-7,8-C2B9H11 (13). Additionally, reactions of 1 with CF3SO3H in the presence of CH3CN or CH3SCN gave 9-CH3C(NH2)-nido-7,8-C2B9H11 (5) and 9-CH3SC(NH2)-nido-7,8-C2B9H11 (6) by electrophilic substitution. (C) 2013 Elsevier B.V. All rights reserved.
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页码：217 / 224
页数：8
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