Low-Valent Chemistry: An Alternative Approach to Phosphorus-Containing Oligomers
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posted on 2014-12-15, 00:00 authored by Stephanie C. Kosnik, Gregory J. Farrar, Erin L. Norton, Benjamin F. T. Cooper, Bobby D. Ellis, Charles L. B. MacdonaldA convenient
preparative approach to low-valent phosphorus-rich oligomers is presented.
Ligand substitution reactions involving anionic diphosphine ligands
of the form [(PR<sub>2</sub>)<sub>2</sub>N]<sup>−</sup> and
[(PPh<sub>2</sub>)<sub>2</sub>C<sub>5</sub>H<sub>3</sub>]<sup>−</sup> and a triphosphenium bromide P<sup>I</sup> precursor result in the
formation of phosphorus(I)-containing heterocycles, several of which
are of types that have never been prepared before. The methodology
described also allows for the preparation of the known heterocycle <i>cyclo</i>-[P(PPh<sub>2</sub>)N(PPh<sub>2</sub>)]<sub>2</sub> in better yields and purity than the synthetic approach reported
previously. Preliminary reactivity studies demonstrate the viability
of such zwitterionic oligomers as multidentate ligands for transition
metals.
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Keywords
zwitterionic oligomersPPhheterocycleLigand substitution reactionstransition metalsPRtypetriphosphenium bromide PI precursor resultviabilitymethodologyAlternative Approachapproachmultidentate ligandsOligomersAformationcyclophosphorusyieldpreparationPreliminary reactivity studiesdiphosphine ligandspurity
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