On the energetics of P-P bond dissociation of sterically strained tetraamino-diphosphanes

Dalton Transactions : an International Journal of Inorganic Chemistry
M BlumD Gudat

Abstract

The homolytic P-P bond fission in a series of sterically congested tetraaminodiphosphanes (R2N)2P-P(NR2)2 ({4}2-{9}2, two of which were newly synthesized and fully characterized) into diaminophosphanyl radicals (R2N)2P˙ (4-9) was monitored by VT EPR spectroscopy. Determination of the radical concentration from the EPR spectra permitted to calculate free dissociation energies ΔGDiss(295) as well as dissociation enthalpies ΔHDiss and entropies ΔSDiss, respectively. Large positive values of ΔGDiss(295) indicate that the degree of dissociation is in most cases low, and the concentration of persistent radicals--even if they are spectroscopically observable at ambient temperature--remains small. Appreciable dissociation was established only for the sterically highly congested acyclic derivative {9}2. Analysis of the trends in experimental data in connection with DFT studies indicate that radical formation is favoured by large entropy contributions and the energetic effect of structural relaxation (geometrical distortions and conformational changes in acyclic derivatives) in the radicals, and disfavoured by attractive dispersion forces. Comparison of the energetics of formation for CC-saturated N-heterocyclic diphosphanes and the 7π-r...Continue Reading

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Citations

Feb 11, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·D Gudat
Jul 23, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Nick A GiffinJason D Masuda
Feb 13, 2020·Angewandte Chemie·Christoph HellingStephan Schulz
Nov 18, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Natalia SzynkiewiczRafał Grubba
May 6, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Callum BranfootPaul G Pringle

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