Year: 2020
Type: preprint
Abstract: Biology uses precise control over proton, electron, H-atom, or H 2 transfer to mediate challenging reactivity. While synthetic complexes have made incredible strides in replicating secondary coordination electron or proton donors, there are comparatively fewer examples of ligands that can mediate both proton and electron storage. Rarer still are ligands that can store full H 2 equivalents. Here we report a dihydrazonopyrrole Ni complex where an H 2 equivalent can be stored on the ligand periphery without any redox change at the metal center. This ligand-based storage of H 2 can be leveraged for catalytic hydrogenations. Kinetic and computational analysis suggests a rate determining H 2 binding step followed by comparatively facile H–H scission to hydrogenate the ligand. This system is an unusual example where a synthetic system can mimic biology’s ability to mediate H 2 transfer via secondary coordination sphere-based processes.
Source: ChemRxiv
Institution: University of Chicago
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
Awards: G102163711, G1055550527, G107546177, G1313983767, G1505794299, G1664757510, NSF's ChemMatCARS: A synchrotron X-ray national facility for chemistry and materials research at the Advanced Photon Source, G1925058530, G2101401529, G2287611682, G262962599, G2887060908, G2959462655, G3031701862, G3075337988, G340565428, G498139845, G5106849484, G513797252, G5607048534, Distal Anion Stabilization of Biologically Relevant Oxo Intermediates, G6848031779, G6918803902, G7047700447, G7368700025, G969889393, G993149817
OpenAlex ID: W3201618463