Experimental and Computational Studies on Quadruply Bonded Dimolybdenum Complexes with Terminal and Bridging Hydride Ligands
| Autor: | Eliseo Ruiz, Natalia Curado, Celia Maya, Ernesto Carmona, Marina Pérez-Jiménez, Santiago Alvarez, Jesús Campos |
|---|---|
| Rok vydání: | 2021 |
| Předmět: | |
| Zdroj: | Chemistry – A European Journal. 27:6569-6578 |
| ISSN: | 1521-3765 0947-6539 |
| DOI: | 10.1002/chem.202004948 |
| Popis: | This contribution focuses on complex [Mo2 (H)2 (μ-AdDipp2 )2 ] (1) and tetrahydrofuran and pyridine adducts [Mo2 (H)2 (μ-AdDipp2 )2 (L)2 ] (1⋅thf and 1⋅py), which contain a trans-(H)Mo≣Mo(H) core (AdDipp2 =HC(NDipp2 )2 ; Dipp=2,6-iPr2 C6 H3 ). Computational studies provide insights into the coordination and electronic characteristics of the central trans-Mo2 H2 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, PMe3 , can bind to 1, causing one of the hydrides to form a three-centered, two-electron (3c-2e) Mo-H→Mo bond (2⋅PMe3 ). 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, AgNTf2 , to afford a monohydride [Mo2 (μ-H)(μ-NTf2 )(μ-AdDipp2 )2 ] (4), with an O,O'-bridging triflimidate ligand. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|