A. Appel, D. Pool, Molly O’Hagan
May 27, 2011
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Influential Citations
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Quality indicators
Journal
ACS Catalysis
Abstract
[Ni(PPh2NBn2)2(CH3CN)]2+ (where PPh2NBn2 is 1,5-dibenzyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane), has been studied as an electrocatalyst for the production of hydrogen in acetonitrile. Strong acids, such as p-cyanoanilinium, protonate [Ni(PPh2NBn2)2(CH3CN)]2+ prior to reduction under catalytic conditions, and an effective pKa of 6.7 ± 0.4 was determined for the protonation product. Through multinuclear NMR spectroscopy studies, the nickel(II) complex was found to be doubly protonated without any observed singly protonated species. In the doubly protonated complex, both protons are positioned exo with respect to the metal center and are stabilized by an N–H–N hydrogen bond. The formation of exo protonated isomers is proposed to limit the rate of hydrogen production because the protons are unable to gain suitable proximity to the reduced metal center to generate H2. Preprotonation of [Ni(PPh2NBn2)2(CH3CN)]2+ has been found to shift the catalytic operating potential to more positive potentials by up...