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Metal-​ligand cooperativity in Pd-​hydroquinone complexes for dioxygen reduction

Horak, Kyle T. and Agapie, Theodor (2014) Metal-​ligand cooperativity in Pd-​hydroquinone complexes for dioxygen reduction. In: 248th American Chemical Society National Meeting & Exposition, August 10-14, 2014, San Francisco, CA.

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The development of selective catalysts for the multiproton-multielectron redn. of small mol. substrates is of significant interest. Metal-ligand cooperativity has been utilized to expand the reactivity of transition metals. To facilitate proton and electron transfer during dioxygen redn., a ligand contg. a redox-active hydroquinone moiety was prepd. A Pd(0)-hydroquinone complex was synthesized and found to rapidly react with dioxygen at room temp. to quant. yield the corresponding Pd(0)-quinone complex. Slower reactivity with dioxygen was obsd. with a (Pd-H)-hydroquinone complex at room temp. to cleanly yield the protonated Pd(0)-quinone complex. Structure-reactivity studies were conducted using a Ag(I)-hydroquinone complex and a Pd(0) complex with a redox-inactive para-methoxy-substituted central arene as probes for ligand-only and Pd-only reactivity resp. The mechanism of dioxygen reaction and product selectivity was studied by variable temp. NMR, gas quantification by Toepler pump, and UV/Vis and soln. IR spectroscopy.

Item Type:Conference or Workshop Item (Paper)
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Agapie, Theodor0000-0002-9692-7614
Additional Information:© 2014 American Chemical Society.
Record Number:CaltechAUTHORS:20140812-110712960
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:48380
Deposited By: Tony Diaz
Deposited On:12 Aug 2014 18:33
Last Modified:03 Oct 2019 07:03

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