Experimental and Computational Studies on Quadruply Bonded Dimolybdenum Complexes with Terminal and Bridging Hydride Ligands.
Chemistry
; 27(21): 6569-6578, 2021 Apr 12.
Article
em En
| MEDLINE
| ID: mdl-33469945
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 ] (1â
thf and 1â
py), which contain a trans-(H)Moâ£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 1â
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-HâMo bond (2â
PMe3 ). A DFT analysis of the terminal and bridging hydride coordination to the Moâ£Mo bond is also reported, along with reactivity studies of the Mo-H bonds of these complexes. Reactions investigated include oxidation of 1â
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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MEDLINE
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En
Ano de publicação:
2021
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Article