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Addressing the Nature of Phosphinidene Sulfides via the Synthesis of P−S Heterocycles
Author(s) -
Graham Cameron M. E.,
Macdonald Charles L. B.,
Boyle Paul D.,
Wisner James A.,
Ragogna Paul J.
Publication year - 2018
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.201705198
Subject(s) - phosphinidene , alkyne , sulfide , sulfur , chemistry , ring (chemistry) , stereochemistry , medicinal chemistry , computational chemistry , organic chemistry , catalysis
The phosphorus–sulfur heterocycles 1,2‐thiaphosphetenes and phosphirene sulfides have been prepared, and represent the first structurally characterized derivatives for either class of compound. These strained P−S ring systems are formed by the reaction of a phosphinidene sulfide and alkyne. Using an internal alkyne, only the 3‐membered P V , phosphirene sulfide was produced, whereas a terminal alkyne yielded a mixture of phosphirene sulfide and 1,2‐thiaphosphetene (P III ). Detailed computational analysis revealed that for numerous derivatives of alkynes, the corresponding 4‐membered rings are always more stable than the 3‐membered isomers. The electronic nature of “free” phosphinidene sulfides (R−P=S) is discussed based on computational results.