Pérez-Jiménez Marina, Curado Natalia, Maya Celia, Campos Jesús, Ruiz Eliseo, Álvarez 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) and University of Sevilla, Avda. Américo Vespucio, 49, 41092, Sevilla, Spain.
Departament de Quimica Inorgànica and Institut de Quimica Teòrica i Computacional, Universitat de Barcelona, Marti i Franquès 1-11, 08028, Barcelona, Spain.
Chemistry. 2021 Apr 12;27(21):6569-6578. doi: 10.1002/chem.202004948. Epub 2021 Mar 10.
This contribution focuses on complex [Mo (H) (μ-Ad ) ] (1) and tetrahydrofuran and pyridine adducts [Mo (H) (μ-Ad ) (L) ] (1⋅thf and 1⋅py), which contain a trans-(H)Mo≣Mo(H) core (Ad =HC(NDipp ) ; Dipp=2,6-iPr C H ). Computational studies provide insights into the coordination and electronic characteristics of the central trans-Mo H unit of 1, with four-coordinate, fourteen-electron Mo atoms and ϵ-agostic interactions with Dipp methyl groups. Small size C- and N-donors give rise to related complexes 1⋅L but only one molecule of P-donors, for example, PMe , can bind to 1, causing one of the hydrides to form a three-centered, two-electron (3c-2e) Mo-H→Mo bond (2⋅PMe ). A DFT analysis of the terminal and bridging hydride coordination to the Mo≣Mo bond is also reported, along with reactivity studies of the Mo-H bonds of these complexes. Reactions investigated include oxidation of 1⋅thf by silver triflimidate, AgNTf , to afford a monohydride [Mo (μ-H)(μ-NTf )(μ-Ad ) ] (4), with an O,O'-bridging triflimidate ligand.
本论文聚焦于复杂化合物[Mo (H) (μ-Ad ) ] (1)以及四氢呋喃和吡啶加合物[Mo (H) (μ-Ad ) (L) ] (1⋅thf和1⋅py)，它们含有一个反式-(H)Mo≣Mo(H)核心（Ad =HC(NDipp ) ；Dipp=2,6-iPr C H ）。计算研究深入探讨了1的中心反式-Mo H单元的配位和电子特性，其中钼原子为四配位、十四电子，并与Dipp甲基存在ϵ-超共轭相互作用。小型的碳和氮供体可生成相关配合物1⋅L，但只有一个磷供体分子，例如PMe ，能与1结合，导致其中一个氢化物形成一个三中心、两电子(3c-2e)的Mo-H→Mo键(2⋅PMe )。本文还报道了对末端和桥连氢化物与Mo≣Mo键配位的密度泛函理论分析，以及这些配合物中Mo-H键的反应性研究。所研究的反应包括用三氟甲磺酸银AgNTf 氧化1⋅thf，得到一个单氢化物[Mo (μ-H)(μ-NTf )(μ-Ad ) ] (4)，其带有一个O,O'-桥连的三氟甲磺酸盐配体。
