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A strong organic electron donor incorporating highly π-donating triphenylphosphonium ylidyl substituents

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Abstract

The π-electron donor strength of a triphenylphosphonium ylidyl group (Ph3P[double bond, length as m-dash]CH–) was explored through its substitution onto a bispyridinylidene (BPY) scaffold. Electrochemical studies revealed that the new triphenylphosphonium ylidyl-substituted BPY is the most reducing di-substituted derivative reported to date (E1/2 = −1.55 V vs. SCE). By using a previously established correlation between the redox potential of the substituted BPYs and the corresponding substituent, a Hammett constant for the Ph3P[double bond, length as m-dash]CH– group was determined (σp+ = −2.33), establishing it as the most donating neutral substituent currently quantified. The BPY is readily oxidized by hexachloroethane to produce the corresponding dicationic bipyridinium salt as a mixture of isomers owing to hindered Cylidyl–Cpyridyl bond rotation. In preliminary tests of the BPY as a reductant, dichlorotricyclohexylphosphorane and chlorodiphenylphosphine were reduced to the corresponding phosphine and diphosphine, respectively.

Graphical abstract: A strong organic electron donor incorporating highly π-donating triphenylphosphonium ylidyl substituents

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Publication details

The article was received on 10 Sep 2019, accepted on 30 Oct 2019 and first published on 30 Oct 2019


Article type: Paper
DOI: 10.1039/C9OB01984G
Org. Biomol. Chem., 2019, Advance Article

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    A strong organic electron donor incorporating highly π-donating triphenylphosphonium ylidyl substituents

    M. M. Burgoyne, T. M. MacDougall, Z. N. Haines, J. W. Conrad, L. A. Calhoun, A. Decken and C. A. Dyker, Org. Biomol. Chem., 2019, Advance Article , DOI: 10.1039/C9OB01984G

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