Two-electron HCl to H2 photocycle promoted by Ni(II) polypyridyl halide complexes. Academic Article

abstract

• Photochemical HX splitting requires the management of two protons and the execution of multielectron photoreactions. Herein, we report a photoinduced two-electron reduction of a polypyridyl Ni(II) chloride complex that provides a route to H2 evolution from HCl. The excited states of Ni complexes are too short to participate directly in HX activation, and hence, the excited state of a photoredox mediator is exploited for the activation of HX at the Ni(II) center. Nanosecond transient absorption (TA) spectroscopy has revealed that the excited state of the polypyridine results in a photoreduced radical that is capable of mediating HX activation by producing a Ni(I) center by halogen-atom abstraction. Disproportionation of the photogenerated Ni(I) intermediate affords Ni(II) and Ni(0) complexes. The Ni(0) center is capable of reacting with HX to produce H2 and the polypyridyl Ni(II) dichloride, closing the photocycle for H2 generation from HCl.

authors

• Powers, David

published proceedings

• J Am Chem Soc

altmetric score

• 1

author list (cited authors)

• Powers, D. C., Anderson, B. L., & Nocera, D. G.

citation count

• 46

complete list of authors

• Powers, David C||Anderson, Bryce L||Nocera, Daniel G

publication date

• December 2013

publisher

• American Chemical Society (ACS)  Publisher

published in

• Journal of the American Chemical Society  Journal

keywords

• Crystallography, X-Ray
• Electrons
• Halogens
• Hydrochloric Acid
• Hydrogen
• Nickel
• Pyridines
• Spectrum Analysis

PubMed Central ID

• 24245545

Digital Object Identifier (DOI)

• 10.1021/ja408787k

start page

• 18876

end page

• 18883

volume

• 135

issue

• 50