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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Synthesis, characterisation and some chemistry of C- and B-substituted carboxylic acids of cobalt bis(dicarbollide)?
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Synthesis, characterisation and some chemistry of C- and B-substituted carboxylic acids of cobalt bis(dicarbollide)?

机译：双（二咔唑钴）钴的C和B取代羧酸的合成，表征和某些化学性质

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摘要

Low temperature reactions of lithiated cobalt bis(1,2-dicarbollide)(1~?) (1~~?) in DME with carbon dioxide leads to the substitution of 1~? at the C-atoms by carboxy function(s). This results in a good yield formation of monosubstituted and disubstituted products of formulations [(1-HOOC-1,2-C_2B_9H_(10))(1',2'-C_2B_9H_(11))- 3,3'-Co)]~? (2~~?) and [(HOOC)_2-(1,2-C_2B_9H_(10))2-3,3'-Co]~? (3a,b~?), respectively. Indeed, the latter compound is in fact a mixture of two diastereoisomers, denoted here as 1,1'-anti (3a~?) and 1,2'-syn-isomer (3b~?), from which only the former major species (3a~?) could be isolated in pure form. Considerations about stereochemistry of these species are supported by geometry optimizations and calculations of 11B NMR shifts at the GIAO-DFT level. In addition, three monocarboxylic acids with three different linear spacers between the carboxy groups and the cage are reported. The first one of the formula [(1-HOOC-CH_2-1,2- C_2B_9H_(10))(1',2'-C_2B_9H_(11))-3,3'-Co]~? (5~?) results in a lithiation followed by reaction with BrCH_2COOEt and hydrolysis of the respective ethyl ester (4~?). Another one with ethylene chain [(1-HOOC-(CH_2)_2-1,2- C_2B_9H_(10))(1',2'-C_2B_9H_(11))-3,3'-Co]~? (6~?) was prepared by the oxidation of a hydroxypropyl derivative of the ion 1~?. The sole representative of B-substituted species of the formulation [8-(HOOC-CH_2-O-1,2- C_2B_9H_(10))(1',2'-C_2B_9H_(11))-3,3'-Co]~? (7~?) is prepared by alkylation of the known 8-hydroxy derivatives of the ion 1~? by BrCH_2COOEt and alkaline hydrolysis. A synthetic route to active nitrofenyl esters (8~?, 9~? and 10~?) is described here based on the respective acids 5~? to 7~?. As verified, the nitrophenyl esters provide easy access to the formation of amidic bonds between the boron cage and organic primary amino functions. Examples of compounds containing butylamide or benzylamide [(1-RNHOC-(CH_2)_n-1,2-C_2B_9H_(10))- (1',2'-C_2B_9H_(11))-3,3'-Co]~? (n = 1,2; R = Bu 11a,b~?, R = Bn: 12a,b~?) end group are described. Also the possibility of inter-connecting two clusters of the anion 1~? via the amidic bond is shown in derivative (13~?). These methods are applicable in the synthesis of a variety of functional molecules, particularly those applicable in drug design, surface modifications, and material science.
机译：锂化的双（1,2-二咔唑）（1〜？）（1 ~~）钴在二氧化碳中的低温反应导致二氧化碳被1〜？取代。在C原子上通过羧基官能团这导致制剂[（1-HOOC-1,2-C_2B_9H_（10））（1'，2'-C_2B_9H_（11））-3,3'-Co）的单取代和双取代产物形成良好的收率。 〜？ （2 ~~？）和[（HOOC）_2-（1,2-C_2B_9H_（10））2-3,3'-Co]〜？ （3a，b〜？）。实际上，后一种化合物实际上是两种非对映异构体的混合物，在这里表示为1,1'-反（3a〜？）和1,2'-syn-异构体（3b〜？），只有前一种主要种类（3a〜？）可以纯净形式分离。几何优化和GIAO-DFT级11B NMR位移的计算支持了有关这些物质立体化学的考虑。另外，据报道在羧基和笼之间具有三个不同的线性间隔基的三种一元羧酸。公式中的第一个[[1-HOOC-CH_2-1,2- C_2B_9H_（10））（1'，2'-C_2B_9H_（11））-3,3'-Co]〜？ （5→）导致锂化，然后与BrCH_2COOEt反应并水解相应的乙酯（4→）。另一个带有乙烯链的[[1-HOOC-（CH_2）_2-1,2-C_2B_9H_（10））（1'，2'-C_2B_9H_（11））-3,3'-Co]〜通过氧化离子1〜α的羟丙基衍生物制备（6〜α）。制剂[8-（HOOC-CH_2-O-1,2- C_2B_9H_（10））（1'，2'-C_2B_9H_（11））-3,3'-Co的唯一代表〜？ （7〜7）是通过将离子1〜2的已知的8-羟基衍生物烷基化而制备的。通过BrCH_2COOEt和碱水解。在此基于各自的酸5〜α描述了合成活性的亚硝基苯甲酸酯（8〜α，9〜α和10〜α）的合成途径。到7〜？如已证实的，硝基苯基酯提供了在硼笼和有机伯氨基官能团之间容易形成酰胺键的途径。含有丁基酰胺或苄基酰胺[（1-RNHOC-（CH_2）_n-1,2-C_2B_9H_（10））-（1'，2'-C_2B_9H_（11））-3,3'-Co]的化合物的实例？ （n ＝ 1，2; R ＝ Bu 11a，b〜α，R ＝ Bn：12a，b〜α）端基被描述。还有可能将阴离子1〜？的两个簇相互连接。经由酰胺键显示为衍生物（13-α）。这些方法适用于各种功能分子的合成，尤其适用于药物设计，表面修饰和材料科学的那些。

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