Do Spiroarsoranes Exhibit Polytopal Equilibrium in Solution?

The spiroarsoranes 5-phenyl-1,6-dioxa-4,9-diaza-5λ5-arsaspiro[4.4]nonane (6), (3R,8R)-3,8-dimethyl-5-phenyl-1,6-dioxa-4,9-diaza-5λ5-arsaspiro[4.4]nonane (7), (2S,7S)-2,7-dimethyl-5-phenyl-1,6-dioxa-4,9-diaza-5λ5-arsaspiro[4.4]nonane (8), and (3S,8S)-3,8-dimethyl-(2R,7R)-2,5,7-triphenyl-1,6-dioxa-4,9...

Full description

Saved in:
Bibliographic Details
Published in:Inorganic chemistry 2010-02, Vol.49 (4), p.1496-1502
Main Authors: Tapia-Benavides, Antonio R, Mendoza-Huizar, Luis H, Pérez-García, Francisco, Tlahuext, Hugo, Alvarez, Alejandro, Tlahuextl, Margarita
Format: Article
Language:English
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The spiroarsoranes 5-phenyl-1,6-dioxa-4,9-diaza-5λ5-arsaspiro[4.4]nonane (6), (3R,8R)-3,8-dimethyl-5-phenyl-1,6-dioxa-4,9-diaza-5λ5-arsaspiro[4.4]nonane (7), (2S,7S)-2,7-dimethyl-5-phenyl-1,6-dioxa-4,9-diaza-5λ5-arsaspiro[4.4]nonane (8), and (3S,8S)-3,8-dimethyl-(2R,7R)-2,5,7-triphenyl-1,6-dioxa-4,9-diaza-5λ5-arsaspiro[4.4]nonane (9) were prepared by reaction of phenylarsonic acid and the correspondig amino alcohol. The presence of polytopal Δ ⇆ Λ equilibrium in 6−9 was demonstrated by HPLC and NMR studies. NBO computations at the MP2/6-31+G(2d,2p) level indicate that methyl substitution in C2 or C3 of the oxazarsolane ring determines the predominance of Δ or Λ stereoisomers. GIAO B3LYP/6-311++G(2d,2p) computations were used to assign experimental 1H and 13C NMR spectra.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic901740d