Photohalogen elimination chemistry in low-valent binuclear nickel complexes

Polyhedron 2021, 203, 115228

The photogeneration of X2is the key to achieving an efficient HX-splitting photocycle, as it is more thermodynamically and kinetically challenging than its H2half reaction counterpart. Here we report a strategy that enables Cl2photoelimination from low-valent binuclear d9–d9and d9–d10Ni complexes. We demonstrate the importance a of metal–metal bond interaction for M–X bond photoactivation with a combination of TD-DFT computations together with spectroscopy and photo crystallography, exemplifying a design principle for future developments of 3d metal complexes for HX photocatalysis

https://www.sciencedirect.com/science/article/pii/S0277538721002102

Seung Jun Hwang¹², Ryan G. Hadt³⁴, Serge Ruccolo^a , David Gygi¹ , Shao-LiangZheng¹ , Yu-Sheng Chen⁵ , Daniel G. Nocera¹

1 Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, MA 02138, USA

2 Department of Chemistry, POSTECH, Pohang 37673, South Korea

3 Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL 60439, USA

4 Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA

5 ChemMatCARS, The University of Chicago, Argonne, IL 60439, USA