ISSN:
0009-2940
Keywords:
Phosphoranes, organofluoro-
;
Spirophosphoranes
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Reactions of Fluorophosphoranes with Trimethylsilyl (Trimethylsilyloxy)acetate: Structures, NMR-Spectroscopic Studies and X-ray Investigations of Mono- and Spirocyclic (Acyloxy)phosphoranes[1]The reaction of the tetrafluorophosphoranes RPF4 (R = Me, Ph) with trimethylsilyl (trimethylsilyloxy)acetate (1) yields the corresponding monocyclic fluoro(acyloxy)phosphoranes 2 and 3 by cleavage of the Si - O bond and elimination of (CH3)3SiF. 2 and 3 were investigated by NMR spectrometry. The spirocyclic (acyloxy)phosphoranes 4-13 are formed analogously by the reaction of 1 with the fluorophosphoranes RPF4 [R = F, Me, Et, iPr, Me3SiCH2, CH2Cl, CHCl2, H2C = CH, C6H5, 2,5-(CH3)2C6H3] in a molar ratio of 2:1. Spirophosphorane 14 is synthesized by the reaction of with PhN3 in the presence of a base. The trifluorophosphoranes R2PF3 (R = Me, Ph) react with 1 to form the monocyclic fluoro(acyloxy)phosphoranes 15 and 16, where the fluorine atom occupies an axial position at trigonal-bipyramidal (TBP) phosphorus. X-ray structure analyses of 4 and 7 reveal TBP geometry at phosphorus. The acyloxy ligand is found to form a chelate ring, whereby one axial and one equatorial site at TBP phosphorus are bridged.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19921250408
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