Metal Tetrahydroborates and Tetrahydroborato Metalates. 30 [1] Solvates of Alcoholato‐, Phenolato‐, and Bis(trimethylsilyl)amido‐Magnesium Tetrahydroborates XMgBH4(Ln). Metall Tetrahydroborate und Tetrahydroborato Metallate, 30 [1]. Solvate der Alkoholato‐, Phenolato‐ und Bis(trimethylsilyl)amino‐ma
Metal Tetrahydroborates and Tetrahydroborato Metalates. 30 [1] Solvates of Alcoholato‐, Phenolato‐, and Bis(trimethylsilyl)amido‐Magnesium Tetrahydroborates XMgBH4(Ln). Metall Tetrahydroborate und Tetrahydroborato Metallate, 30 [1]. Solvate der Alkoholato‐, Phenolato‐ und Bis(trimethylsilyl)amino‐ma
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金属四氢硼酸盐和四氢硼酸金属盐 30 [1] 醇合、酚酸和双（三甲基甲硅烷基）氨基镁四氢硼酸盐 XMgBH4(Ln) 的溶剂化物，金属四氢硼酸盐和四氢硼酸金属盐，30 [1]。嘛
DOI：
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发表时间：
2005
期刊：
影响因子：
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通讯作者：
G. Wagner
中科院分区：
文献类型：
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作者：
M. Bremer;G. Linti;H. Nöth;Martina Thomann;G. Wagner
通过ROH (R = Me, Et, iPr, tBu, CH2CMe3, Et2(tBu)C, Ph3C, Ph, 2,4,6 - me3c6h2, (2,6 -iPr)2C6H3, (2,6 - tbu2)C6H3, 2-(iPrO)C6H4, 2,6 -(MeO)2C6H3)与EtMg（BH4）的乙醚溶液1:1反应，制备了一系列醇型和酚型四氢硼酸镁溶剂（RO）Mg(BH4)（OEt2）。二乙醚被thf、dme和二lyme置换生成各种溶剂化物（RO）Mg(BH4)(L)n （L = thf、dme、二lyme， n = 1,2,3）。这些化合物大多是中心对称的二聚体，中心有一个Mg2O2四元环。不管其组成如何，11B核磁共振信号都是1:4:6:4:1的五重奏，这表明BH4基团的氢原子在磁力上是等效的。测定了8种化合物[(RO)Mg(BH4)(OEt2)]2 (R = iPr, tBu, tBuCH2, Et3C, Me3Si), [(PhO)Mg(BH4)(thf)2]2, (2,6 - tbu2c6h30)Mg(BH4)(thf)2, (2,6 - tbu2c6h30)-Mg(BH4)（thf)(dme)）的分子结构。所有化合物的典型特征是六配位的镁原子。单核配合物具有双齿BH4基团，而双核配合物具有双或三齿BH4基团，这取决于配位O原子的数量。
A series of alcoholato and phenolato magnesium tetrahydroborates have been prepared as solvates (RO)Mg(BH4)(OEt2) by 1:1 reactions of ROH (R = Me, Et, iPr, tBu, CH2CMe3, Et2(tBu)C, Ph3C, Ph, 2, 4, 6-Me3C6H2, (2, 6-iPr)2C6H3, (2, 6-tBu2)C6H3, 2-(iPrO)C6H4, 2, 6-(MeO)2C6H3) with diethyl ether solutions of EtMg(BH4). Displacement of diethyl ether by thf, dme, and diglyme produced various solvates (RO)Mg(BH4)(L)n (L = thf, dme, diglyme, n = 1, 2, 3). Most of these compounds are centrosymmetric dimers with a central Mg2O2 four membered ring. Irrespective of the composition, the 11B NMR signals are 1:4:6:4:1 quintets showing that the hydrogen atoms of the BH4 groups are magnetically equivalent. The molecular structure of eight compounds [(RO)Mg(BH4)(OEt2)]2 (R = iPr, tBu, tBuCH2, Et3C, Me3Si), [(PhO)Mg(BH4)(thf)2]2, (2, 6-tBu2C6H3O)Mg(BH4)(thf)2, (2, 6-tBu2C6H3O)-Mg(BH4)(thf)(dme)) have been determined. Typical for all compounds are hexacoordinated Mg atoms. The mononuclear complexes feature bidentate BH4 groups while dinuclear species show di- or tridentate BH4 groups depending on the number of coordinated O atoms.
Mononuclear species are obtained only for compounds with bulky R groups, e. g. 2, 6-(tBu2)(C6H3O)Mg(BH4)(thf)2 with tridentate BH4 groups. This compound has a linear O-C-Mg unit. In Me2SO the compound [(2-iPrO)C6H4O]Mg(BH4)(OEt2) underwent ligand exchange to produce [(2-iPrO)C6H4O]2Mg(OSMe2)]2.
Reaction of EtMgBH4 with a stoichiometric amount (1:1) of (Me3Si)2NH gives [((Me3Si)2N)-Mg(BH4)(OEt2)]2, 46 with a tridentate BH4 group. Its diethyl ether molecule can be replaced by thf, dme and diglyme. Amongst these solvates the compound [(Me3Si)2N]Mg(BH4)(diglyme) is mononuclear and its structure shows a bidentate BH4 group. Compound 46 on repeated crystallization from diethyl ether is transformed into [(Me3SiO)Mg(BH4)(OEt2)]2.
No compound with a BH4 group bonded to two Mg atoms has so far been found.