从金属氢化物到金属硼氢化物,Inorganic Chemistry

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从金属氢化物到金属硼氢化物
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2018-08-23 00:00:00 , DOI: 10.1021/acs.inorgchem.8b01398
Bo Richter ₁ , Jakob B. Grinderslev ₁ , Kasper T. Møller _{1,

2} , Mark Paskevicius _{1,

2} , Torben R. Jensen ₁

Affiliation

从金属氢化物开始，提出了适用于多种金属硼氢化物及其溶剂化物的通用合成，纯化和去溶剂化方法。针对11种不同的金属硼氢化物M（BH ₄）_n（M = Li，Na，Mg，Ca，Sr，Ba，Y，Nd，Sm，Gd，Yb）提供了一种优化的通用合成方法超过15种不同的多晶型物和20多种金属硼氢化物溶剂化物配合物。商业上不可用的金属氢化物（MH _n，M ＝ Sr，Ba，Y，Nd，Sm，Gd，Yb）是利用高压氢化合成的。为了合成金属硼氢化物，在与二甲基硫醚硼烷反应之前，将所有氢化物进行机械化学活化。设计了一种纯化工艺，以及用于溶剂化物配合物的互补去溶剂工艺，可生产高纯度的产品。以这种方式合成了多晶型纯金属硼氢化物的阵列，支持了该方法的普遍适用性。此外，新的金属硼氢化物α-，α'-β-，γ-Yb（BH ₄）₂，α-Nd（BH ₄）₃和新的溶剂化物Sr（BH ₄）₂ ·1THF，Sm（BH ₄）₂ ·1THF，Yb（BH ₄）₂ · x THF，x = 1或2，Nd（BH ₄）₃ ·1Me ₂ S，Nd（BH ₄）₃ ·1.5THF，Sm（BH ₄）₃ ·1.5THF和Yb（BH ₄）₃ · x Me ₂ S（“ x” =未指定），在此处显示。为每种金属分别优化了合成条件，从而洞悉了反应性和机理。该反应遵循亲核加成/氢化物转移机理。因此，该反应对于离子和极性共价金属氢化物最有效。所呈现的合成方法具有广泛的适用性，这是通过允许轻松访问大量材料并通过按比例放大LiBH _4的合成来证明的。

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From Metal Hydrides to Metal Borohydrides

Commencing from metal hydrides, versatile synthesis, purification, and desolvation approaches are presented for a wide range of metal borohydrides and their solvates. An optimized and generalized synthesis method is provided for 11 different metal borohydrides, M(BH₄)_n, (M = Li, Na, Mg, Ca, Sr, Ba, Y, Nd, Sm, Gd, Yb), providing controlled access to more than 15 different polymorphs and in excess of 20 metal borohydride solvate complexes. Commercially unavailable metal hydrides (MH_n, M = Sr, Ba, Y, Nd, Sm, Gd, Yb) are synthesized utilizing high pressure hydrogenation. For synthesis of metal borohydrides, all hydrides are mechanochemically activated prior to reaction with dimethylsulfide borane. A purification process is devised, alongside a complementary desolvation process for solvate complexes, yielding high purity products. An array of polymorphically pure metal borohydrides are synthesized in this manner, supporting the general applicability of this method. Additionally, new metal borohydrides, α-, α′- β-, γ-Yb(BH₄)₂, α-Nd(BH₄)₃ and new solvates Sr(BH₄)₂·1THF, Sm(BH₄)₂·1THF, Yb(BH₄)₂·xTHF, x = 1 or 2, Nd(BH₄)₃·1Me₂S, Nd(BH₄)₃·1.5THF, Sm(BH₄)₃·1.5THF and Yb(BH₄)₃·xMe₂S (“x” = unspecified), are presented here. Synthesis conditions are optimized individually for each metal, providing insight into reactivity and mechanistic concerns. The reaction follows a nucleophilic addition/hydride-transfer mechanism. Therefore, the reaction is most efficient for ionic and polar-covalent metal hydrides. The presented synthetic approaches are widely applicable, as demonstrated by permitting facile access to a large number of materials and by performing a scale-up synthesis of LiBH₄.

更新日期：2018-08-23

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