Perez-Jimenez Marina, Curado Natalia, Maya Celia, Campos Jesus, Jover Jesus, Alvarez Santiago, Carmona Ernesto
Instituto de Investigaciones Químicas (IIQ), Departamento de Química Inorgánica and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Consejo Superior de Investigaciones Científicas (CSIC), University of Sevilla, Avda. Américo Vespucio, 49, 41092 Sevilla, Spain.
Department de Química Inorgànica i Orgànica, Secció de Química Inorgànica, and Institut de Química Teòrica i Computacional, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Spain.
J Am Chem Soc. 2021 Apr 7;143(13):5222-5230. doi: 10.1021/jacs.1c01602. Epub 2021 Mar 23.
The reactions of LiAlH as the source of LiH with complexes that contain (H)Mo≣Mo and (H)Mo≣Mo(H) cores stabilized by the coordination of bulky Ad ligands result in the respective coordination of one and two molecules of (thf)LiH, with the generation of complexes exhibiting one and two HLi(thf)H ligands extending across the Mo≣Mo bond (Ad = HC(NDipp); Dipp = 2,6-PrCH; thf = tetrahydrofuran, CHO). A theoretical study reveals the formation of Mo-H-Li three-center-two-electron bonds, supplemented by the coordination of the Mo≣Mo bond to the Li ion. Attempts to construct a [Mo{HLi(thf)H}(Ad)] molecular architecture led to spontaneous trimerization and the formation of a chiral, hydride-rich MoLiH supramolecular organization that is robust enough to withstand the substitution of lithium-solvating molecules of tetrahydrofuran by pyridine or 4-dimethylaminopyridine.
作为LiH来源的LiAlH与含有由庞大的Ad配体配位稳定的(H)Mo≣Mo和(H)Mo≣Mo(H)核心的配合物反应，分别导致一分子和两分子的(thf)LiH配位，生成具有一个和两个横跨Mo≣Mo键延伸的HLi(thf)H配体的配合物（Ad = HC(NDipp)；Dipp = 2,6-PrCH；thf = 四氢呋喃，CHO）。一项理论研究揭示了Mo-H-Li三中心两电子键的形成，并辅以Mo≣Mo键与Li离子的配位。构建[Mo{HLi(thf)H}(Ad)]分子结构的尝试导致自发三聚，并形成了一种手性、富含氢化物的MoLiH超分子结构，其坚固程度足以承受四氢呋喃的锂溶剂化分子被吡啶或4-二甲基氨基吡啶取代。
