Abstract
A comparative study of amino phenoxide zirconium catalysts in the hydrophosphination of alkenes with diphenylphosphine reveals enhanced activity upon irradiation during catalysis, with conversions up to 10-fold greater than reactions in ambient light. The origin of improved reactivity is hypothesized to result from substrate insertion upon an n→d charge transfer of a Zr–P bond in the excited state of putative phosphido (Zr–PR2) intermediates. TD-DFT analysis reveals the lowest lying excited state in the proposed active catalysts are dominated by a P 3p→Zr 4d MLCT, presumably leading to enhanced catalysis. This hypothesis follows from triamidoamine-supported zirconium catalysts but demonstrates the generality of photocatalytic hydrophosphination with d0 metals.
Highlights
Organophosphines have found extensive use in the areas of materials science, biology, agriculture, electronics, and especially, catalysis [1,2,3,4,5,6,7]
Photolysis has been demonstrated to increase the activity of triamidoamine zirconium compounds for hydrophosphination catalysis while unlocking reactivity with previously inert substrates [31,32,33]
Analysis by time-dependent density functional theory (TD-DFT) suggests the enhanced reactivity under photolysis is due to the population of a chargetransfer state that exhibits significant σ* character and weakening of the Zr–P bond that allows more facile substrate insertion [31]
Summary
Organophosphines have found extensive use in the areas of materials science, biology, agriculture, electronics, and especially, catalysis [1,2,3,4,5,6,7]. Effect of Photolysis on Zirconium Amino Phenoxides for the Hydrophosphination of Alkenes: Improving Catalysis. Photolysis has been demonstrated to increase the activity of triamidoamine zirconium compounds for hydrophosphination catalysis while unlocking reactivity with previously inert substrates [31,32,33].
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