Please use this identifier to cite or link to this item: https://doi.org/10.1021/ic010935w
Title: Apical versus equatorial disposition of substituents in tetraoxyphosphoranes bearing a 1,3,2-dioxaphosphocin ring: Implications on apicophilicity in trigonal bipyramidal phosphorus
Authors: Kommana, P.
Kumaraswamy, S.
Vittal, J.J. 
Kumara Swamy, K.C.
Issue Date: 6-May-2002
Citation: Kommana, P., Kumaraswamy, S., Vittal, J.J., Kumara Swamy, K.C. (2002-05-06). Apical versus equatorial disposition of substituents in tetraoxyphosphoranes bearing a 1,3,2-dioxaphosphocin ring: Implications on apicophilicity in trigonal bipyramidal phosphorus. Inorganic Chemistry 41 (9) : 2356-2363. ScholarBank@NUS Repository. https://doi.org/10.1021/ic010935w
Abstract: New spirocyclic (amino/amido)tetraoxyphosphoranes CH2(6-t-Bu-4-Me-C6 H2O)2P(NRR′) (O2C6Cl4) [R = Me, R′ = Ph (1), R = R′ = i-Pr (2); R = R′ = H (3); R = H, R′ = Ph (4)] and the isothiocyanatotetraoxyphosphorane CH2(6-t-Bu-4-Me-C6H2O)2P (NCS)(O2C6Cl4) (5) have been synthesized. X-ray crystallography for these compounds reveals that -N(Me)Ph, -N(i-Pr)2, and -NCS groups occupy an apical position whereas -NH2 and -NHPh groups occupy an equatorial position in a trigonal bipyramidal geometry around phosphorus. These results are in contrast with the common assumption that a sterically bulky and less electronegative substituent [e.g. -N(i-Pr)2] should be less apicophilic than a sterically small and more electronegative substituent (e.g. -NH2). The possible rationalization for these results is discussed. Variable-temperature (1H, 31P) NMR spectra of these compounds show some unusual features not reported before for pentacoordinate phosphorus. Probable intramolecular processes involving (i) apical- equatorial ↔ equatorial-apical exchange, (ii) apical-equatorial ↔ equatorial-equatorial exchange, and (iii) boat-chair ↔ tub (for the eight-membered ring) interconversion as well as cessation of the P-N bond rotation have been invoked to explain the spectral features.
Source Title: Inorganic Chemistry
URI: http://scholarbank.nus.edu.sg/handle/10635/93124
ISSN: 00201669
DOI: 10.1021/ic010935w
Appears in Collections:Staff Publications

Show full item record
Files in This Item:
There are no files associated with this item.

SCOPUSTM   
Citations

34
checked on Oct 18, 2018

WEB OF SCIENCETM
Citations

34
checked on Oct 2, 2018

Page view(s)

15
checked on Jul 6, 2018

Google ScholarTM

Check

Altmetric


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.