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Phosphaketenes as Building Blocks for the Synthesis of Triphospha Heterocycles
Author(s) -
Heift Dominikus,
Benkő Zoltán,
Grützmacher Hansjörg
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201403419
Subject(s) - chemistry , heteroatom , delocalized electron , silylation , reactivity (psychology) , stereochemistry , atom (system on chip) , medicinal chemistry , ring (chemistry) , organic chemistry , catalysis , medicine , alternative medicine , pathology , computer science , embedded system
Unsaturated phosphorus compounds, such as phosphaalkenes and phosphaalkynes, show a versatile reactivity in cycloadditions. Although phosphaketenes (RPCO) have been known for three decades, their chemistry has remained limited. Herein, we show that heteroatom‐substituted phosphaketenes, R 3 EPCO (E=Si, Sn), are building blocks for silyl‐ and stannyl‐substituted five‐membered heterocycles containing three phosphorous atoms. The structure of the heterocyclic anion depends on the nature of the tetrel atom involved. Although the silyl analogue [P 3 C 2 (OSiR 3 ) 2 ] − is an aromatic 1,2,4‐triphospholide, the stannyl compound [P(CO) 2 (PSnR 3 ) 2 ] − is a 1,2,4‐triphosphacyclopenta‐3,5‐dionate with a delocalized OCPCO fragment. Because of their anionic character, these compounds can easily be used as building blocks, for example, in the preparation of a silyl‐functionalized hexaphosphaferrocene or the parent 1,2,4‐triphosphacyclopenta‐3,5‐dionate [P(CO) 2 (PH) 2 ] − . NMR spectroscopic investigations and computations have shown that the heterocycle‐formation reactions presented herein are remarkably complex.