Experimental and Computational Studies on Quadruply Bonded Dimolybdenum Complexes with Terminal and Bridging Hydride Ligands |
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| Authors: | Marina Pérez-Jiménez Dr Natalia Curado Dr Celia Maya Dr Jesús Campos Prof Dr Eliseo Ruiz Prof Dr Santiago Álvarez Prof Ernesto Carmona |
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| Institution: | 1. 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;2. Departament de Quimica Inorgànica and Institut de Quimica Teòrica i Computacional, Universitat de Barcelona, Marti i Franquès 1–11, 08028 Barcelona, Spain |
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| Abstract: | 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-iPr2C6H3). Computational studies provide insights into the coordination and electronic characteristics of the central trans-Mo2H2 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. |
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| Keywords: | CO2 reduction dimolybdenum complexes hydrides metal–metal interactions quadruple bond |
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