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Triorganylphosphoranides: Realization of an Unusual Structural Motif Utilizing Electron Withdrawing Pentafluoroethyl Groups.
- Source :
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ChemPlusChem [Chempluschem] 2023 Jul; Vol. 88 (7), pp. e202200436. Date of Electronic Publication: 2023 Jan 31. - Publication Year :
- 2023
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Abstract
- Phosphoranides comprising three phosphorus carbon bonds are scarcely represented in the literature. We now utilized tris(pentafluoroethyl)phosphane, P(C <subscript>2</subscript> F <subscript>5</subscript> ) <subscript>3</subscript> , and cyanobis(pentafluoroethyl)phosphane, P(C <subscript>2</subscript> F <subscript>5</subscript> ) <subscript>2</subscript> (CN), featuring electron withdrawing pentafluoroethyl groups, to synthesize such compounds. Metal fluorides MF (M=Ag, Cs) add to P(C <subscript>2</subscript> F <subscript>5</subscript> ) <subscript>3</subscript> yielding respective M[P(C <subscript>2</subscript> F <subscript>5</subscript> ) <subscript>3</subscript> F] salts. Those M[P(C <subscript>2</subscript> F <subscript>5</subscript> ) <subscript>3</subscript> F] subsequently suffer a loss of C <subscript>2</subscript> F <subscript>4</subscript> , furnishing M[P(C <subscript>2</subscript> F <subscript>5</subscript> ) <subscript>2</subscript> F <subscript>2</subscript> ]. The cesium salt decomposes instantaneously when warmed to rt, whereas the silver salt decomposes slowly over several days at rt. Treatment of Ag[P(C <subscript>2</subscript> F <subscript>5</subscript> ) <subscript>3</subscript> F] with 2,2'-bipyridine facilitated the isolation and structural characterization of [Ag(bipy){P(C <subscript>2</subscript> F <subscript>5</subscript> ) <subscript>3</subscript> F}]. With P(C <subscript>2</subscript> F <subscript>5</subscript> ) <subscript>2</subscript> (CN), AgF reacts under substitution of the cyano group yielding P(C <subscript>2</subscript> F <subscript>5</subscript> ) <subscript>2</subscript> F, rather than phosphoranide formation. However, [K(18-crown-6)]F adds to P(C <subscript>2</subscript> F <subscript>5</subscript> ) <subscript>2</subscript> (CN) furnishing [K(18-crown-6)][P(C <subscript>2</subscript> F <subscript>5</subscript> ) <subscript>2</subscript> (CN)F]. Its structural characterization was successful, despite its tendency to undergo an exchange of substituents, yielding [K(18-crown-6)][P(C <subscript>2</subscript> F <subscript>5</subscript> ) <subscript>2</subscript> F <subscript>2</subscript> ] and presumably [K(18-crown-6)][P(C <subscript>2</subscript> F <subscript>5</subscript> ) <subscript>2</subscript> (CN) <subscript>2</subscript> ]. The latter forms an equilibrium with [K(18-crown-6)]CN and P(C <subscript>2</subscript> F <subscript>5</subscript> ) <subscript>2</subscript> (CN) which lies well on side of the phosphane and cyanide salt.<br /> (© 2023 The Authors. ChemPlusChem published by Wiley-VCH GmbH.)
Details
- Language :
- English
- ISSN :
- 2192-6506
- Volume :
- 88
- Issue :
- 7
- Database :
- MEDLINE
- Journal :
- ChemPlusChem
- Publication Type :
- Academic Journal
- Accession number :
- 36719995
- Full Text :
- https://doi.org/10.1002/cplu.202200436