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Please use this identifier to cite or link to this item: http://dspace.library.iitb.ac.in/jspui/handle/10054/3915

Title: Intramolecular amine-induced [1,3]-sigmatropic rearrangement in the reactions of aminophosphinites or phosphites with elemental sulfur or selenium
Authors: CHANDRASEKARAN, P
MAGUE, JT
BALAKRISHNA, MS
Keywords: chalcogen-chalcogen interactions
x-ray structures
molecular-structures
coordination-complexes
phosph(iii)azane macrocycle
phosphinoselenoic chlorides
structural-characterization
cyclodiphosphazane ligands
theoretical investigations
organoselenium compounds
Issue Date: 2006
Publisher: AMER CHEMICAL SOC
Citation: INORGANIC CHEMISTRY, 45(15), 5893-5897
Abstract: Ether- and thioether-functionalized cyclodiphosphazanes cis-[(BuNP)-Bu-t(OCH2CH2EMe)](2) (E = O, 1; E = S, 2) react with 2 equiv of elemental sulfur or selenium to produce dichalcogenides cis-[(BuNP)-Bu-t(E)(OCH2CH2EMe)]2 (4-6), whereas the similar reaction of amine-functionalized cyclodiphosphazane cis-[(BuNP)-Bu-t(OCH2CH2NMe2)](2) (3) with elemental chalcogen results in the formation of thio- or selenophosphates trans-[(BuNP)-Bu-t(O)(ECH2CH2NMe2)](2) (E = S, 7; E = Se, 8) through [1,3]-sigmatropic rearrangement. The X-ray crystal structure of 8 confirms the rearranged product as the trans isomer with a planar P2N2 ring. The equimolar reaction of P(OCH2CH2OMe)(3) (9) with elemental sulfur or selenium produces the simple sulfide and selenide E=P(OCH2CH2OMe)(3) (E = S, 11; E = Se, 12) derivatives, respectively. In contrast, the reaction between P(OCH2CH2NMe2)(3) (10) and S or Se furnishes the rearranged products (13 and 14). The rearrangement reaction was monitored by (PNMR)-P-31 spectroscopy, which confirms the formation of selenophosphinic acid as the first step of the rearrangement. The [1,3]-sigmatropic rearrangement presumably takes place through chalcogen-nitrogen interactions.
URI: http://dx.doi.org/10.1021/ic060413m
http://dspace.library.iitb.ac.in/xmlui/handle/10054/3915
http://hdl.handle.net/10054/3915
ISSN: 0020-1669
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