Relevance of the Electronegativity of Boron in eta~5-Coordinating Ligands:Regioselective Monoalkylation and Monoarylation in Cobaltabisdicarbollide [3,3'-Co(1,2-C_2B_9H_11)_2]~-Clusters

Isabel Rojo; Francesc Teixidor; Clara Vinas; Raikko Kivekas; Reijo Sillanpaa

首页> 外文期刊>Chemistry: A European journal >Relevance of the Electronegativity of Boron in eta~5-Coordinating Ligands:Regioselective Monoalkylation and Monoarylation in Cobaltabisdicarbollide [3,3'-Co(1,2-C_2B_9H_11)_2]~-Clusters

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Relevance of the Electronegativity of Boron in eta~5-Coordinating Ligands:Regioselective Monoalkylation and Monoarylation in Cobaltabisdicarbollide [3,3'-Co(1,2-C_2B_9H_11)_2]~-Clusters

机译：硼在eta〜5配体中的电负性的相关性：钴双双糖脂[3,3'-Co（1,2-C_2B_9H_11）_2]〜-簇中的区域选择性单烷基化和单芳基化

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Regioselective monoalkylation and monoarylation in cobaltabisdicarbollide clusters has been achieved starting from Cs[8-I-3,3'-Co(1,2-C_2B_9H-10)(1',2'-C_2B_9H_11)]by cross-cou-pling reactions between a B-1 fragment and an appropriate Grignard reagent in the presence of a Pd catalyst and Cul.A considerable number of monoalkylated and monoarylated derivatives have been synthesized,which allowed study of the influence of boron in metallocene-type ligands and the effect of alkyl and aryl substituents on boron in boron anionic clusters.Experimental data from UV/Vis spectroscopy,E_1/2 measurements,and X-ray diffraction analysis,and supported by EHMO and ab initio analyses,indicate that the participation of metal d orbitals in the HOMO is less than that in typical metallocene complexes.This canbe explained in terms of the lower electronegativity of boron compared to carbon.Related to this is the -I character of alkyl groups when bonded to boron in boron anionic clusters,contrary to the common belief that alkyl groups are generally electron-releasing moieties.

机译：通过交叉偶联反应，从Cs [8-I-3,3'-Co（1,2-C_2B_9H-10）（1'，2'-C_2B_9H_11）]开始实现了钴双双糖脂簇中的区域选择性单烷基化和单芳基化。在Pd催化剂和Cul的存在下，B-1片段与适当的Grignard试剂之间进行了合成。已合成了大量的单烷基化和单芳基化衍生物，从而可以研究硼对茂金属型配体的影响以及硼阴离子簇中硼上的烷基和芳基取代基。来自UV / Vis光谱，E_1 / 2测量和X射线衍射分析的实验数据，并得到EHMO和从头算分析的支持，表明金属d轨道参与了HOMO小于典型的茂金属络合物中的HOMO。这可以用硼与碳相比更低的电负性来解释。与此有关的是烷基在硼阴离子簇中与硼键合时的-I特性，与普通n认为烷基通常是释放电子的部分。

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《Chemistry: A European journal》 |2003年第18期|共13页
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Isabel Rojo; Francesc Teixidor; Clara Vinas; Raikko Kivekas; Reijo Sillanpaa;
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正文语种 eng
中图分类化学;
关键词
cobalt; b-c coupling; charge transfer; cross-coupling; isolobal relationship;

机译：钴;b-c耦合;电荷转移;交叉耦合;等叶关系;

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1. Relevance of the Electronegativity of Boron in eta~5-Coordinating Ligands:Regioselective Monoalkylation and Monoarylation in Cobaltabisdicarbollide [3,3'-Co(1,2-C_2B_9H_11)_2]~-Clusters [J] . Isabel Rojo, Francesc Teixidor, Clara Vinas, Chemistry: A European journal . 2003,第18期

机译：硼在eta〜5配体中的电负性的相关性：钴双双糖脂[3,3'-Co（1,2-C_2B_9H_11）_2]〜-簇中的区域选择性单烷基化和单芳基化
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3. Structural studies of organoboron compounds LXVIII. C-(2-hydroxyaryl)-N-(2-hydroxyphenylmethyl)nitrones as regioselective bidentate ligands in boron chelate formation. Crystal and molecular structures of a diphenylboron complex and its parent ligand [J] . Kliegel W., Rettig SJ., Trotter J., Canadian Journal of Chemistry . 1998,第7期

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4. Concerted Two-Electron Transfer and Metal-Metal Bond Breaking in Ligand-Bridged Binuclear Complexes.Relevance to Nitrogen Fixation [C] . Darrell Uhrhammer, Franklin A.Schultz The Meeting of the Electrochemical Society . 2001

机译：协调双电子转移和金属 - 金属粘合在配体桥接的双核络合物中断裂。氮固定
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机译：大多面体含硼簇化学。配体诱导的集群间键合亲密度的双电子变化。 19个顶点（η（5）-C5me5）HIrB18H19（pme2ph）和相关卡宾配合物（η（5）-C5me5）HIrB18H19 {C（NHme）（2）}的结构
8. Reactions at the Metal Vertex of a Monometal Metallocarborane Cluster. The Chemistry of (closo-3,3-(PPh3)2-3-(HSO4)-3,1,2-RhC2B9H11) and (closo-3-(PPh3)-3,3-(NO3)-3,1,2RhC2B9H11). [R] . Kalb, W. C., Demidowicz, Z., Speckman, D. M., 1982

机译：单金属金属碳硼烷簇的金属顶点的反应。化学（closo-3,3-（pph3）2-3-（HsO4）-3,1,2-RhC2B9H11）和（closo-3-（pph3）-3,3-（NO3）-3,1），2RhC2B9H11）。

Relevance of the Electronegativity of Boron in eta~5-Coordinating Ligands:Regioselective Monoalkylation and Monoarylation in Cobaltabisdicarbollide [3,3'-Co(1,2-C_2B_9H_11)_2]~-Clusters

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