Splitting of multiple hydrogen molecules by bioinspired diniobium metal complexes: a DFT study

Splitting of molecular hydrogen (H 2 ) into bridging and terminal hydrides is a common step in transition metal chemistry. Herein, we propose a novel organometallic platform for cleavage of multiple H 2 molecules, which combines metal centers capable of stabilizing multiple oxidation states, and lig...

Full description

Saved in:
Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2021-01, Vol.5 (3), p.84-849
Main Authors: Fantuzzi, Felipe, Nascimento, Marco Antonio Chaer, Ginovska, Bojana, Bullock, R. Morris, Raugei, Simone
Format: Article
Language:English
Subjects:
Amines
Cartesian coordinates
Coordination compounds
Ductile-brittle transition
Hydrogen
Hydrogen atoms
Ligands
Oxidation
Quantum chemistry
Splitting
Thermochemical properties
Transition metals
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Splitting of molecular hydrogen (H 2 ) into bridging and terminal hydrides is a common step in transition metal chemistry. Herein, we propose a novel organometallic platform for cleavage of multiple H 2 molecules, which combines metal centers capable of stabilizing multiple oxidation states, and ligands bearing positioned pendant basic groups. Using quantum chemical modeling, we show that low-valent, early transition metal diniobium( ii ) complexes with diphosphine ligands featuring pendant amines can favorably uptake up to 8 hydrogen atoms, and that the energetics are favored by the formation of intramolecular dihydrogen bonds. This result suggests new possible strategies for the development of hydrogen scavenger molecules that are able to perform reversible splitting of multiple H 2 molecules. A novel organometallic platform for activation and splitting of multiple H 2 molecules is investigated by quantum chemical calculations.
ISSN:1477-9226
1477-9234
DOI:10.1039/d0dt03411h