Catalytic hydrogenation enabled by ligand-based storage of hydrogen

• Published in: Chemical communications (Cambridge, England) Vol. 57; no. 32; pp. 3869 - 3872
• Main Authors: McNeece, Andrew J, Jesse, Kate A, Filatov, Alexander S, Schneider, Joseph E, Anderson, John S
• Format: Journal Article
• Language: English
• Published: CAMBRIDGE Royal Soc Chemistry 25.04.2021; Royal Society of Chemistry; Royal Society of Chemistry (RSC)
• Subjects: Biology; Catalysis; Chemistry; Chemistry, Multidisciplinary; Cleavage; Crystallography; Hydrogenation; Ligands; Physical Sciences; Science & Technology
• ISSN: 1359-7345; 1364-548X; 1364-548X
• DOI: 10.1039/d0cc08236h

Biology employs exquisite control over proton, electron, H-atom, or H 2 transfer. Similar control in synthetic systems has the potential to facilitate efficient and selective catalysis. Here we report a dihydrazonopyrrole Ni complex where an H 2 equivalent can be stored on the ligand periphery without metal-based redox changes and can be leveraged for catalytic hydrogenations. Kinetic and computational analysis suggests ligand hydrogenation proceeds by H 2 association followed by H-H scission. This complex is an unusual example where a synthetic system can mimic biology's ability to mediate H 2 transfer via secondary coordination sphere-based processes. Using inspiration from biological cofactors, the reversible storage of hydrogen on a supporting dihydrazonopyrrole ligand enables catalytic hydrogenation reactivity with nickel.