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Kommana P, Kumaraswamy S, Vittal JJ, et al. Apical versus equatorial disposition of substituents in tetraoxyphosphoranes bearing a 1,3,2-dioxaphosphocin ring: implications on apicophilicity in trigonal bipyramidal phosphorus. Inorg Chem. 2002;41(9):2356-63doi: 10.1021/ic010935w.
Kommana, P., Kumaraswamy, S., Vittal, J. J., & Kumara Swamy, K. C. (2002). 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), 2356-63. https://doi.org/10.1021/ic010935w
Kommana, Praveen, et al. "Apical versus equatorial disposition of substituents in tetraoxyphosphoranes bearing a 1,3,2-dioxaphosphocin ring: implications on apicophilicity in trigonal bipyramidal phosphorus." Inorganic chemistry vol. 41,9 (2002): 2356-63. doi: https://doi.org/10.1021/ic010935w
Kommana P, Kumaraswamy S, Vittal JJ, Kumara Swamy KC. Apical versus equatorial disposition of substituents in tetraoxyphosphoranes bearing a 1,3,2-dioxaphosphocin ring: implications on apicophilicity in trigonal bipyramidal phosphorus. Inorg Chem. 2002 May 06;41(9):2356-63. doi: 10.1021/ic010935w. PMID: 11978098.
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Inorg Chem. 2002 May 06;41(9):2356-63. doi: 10.1021/ic010935w.

Apical versus equatorial disposition of substituents in tetraoxyphosphoranes bearing a 1,3,2-dioxaphosphocin ring: implications on apicophilicity in trigonal bipyramidal phosphorus.

Inorganic chemistry

Praveen Kommana, Sudha Kumaraswamy, J J Vittal, K C Kumara Swamy

Affiliations

  1. School of Chemistry, University of Hyderabad, Hyderabad-500046, A. P., India.

PMID: 11978098 DOI: 10.1021/ic010935w

Abstract

New spirocyclic (amino/amido)tetraoxyphosphoranes CH(2)(6-t-Bu-4-Me-C(6)H(2)O)(2)P(NRR')(O(2)C(6)Cl(4)) [R = Me, R' = Ph (1), R = R' = i-Pr (2); R = R' = H (3); R = H, R' = Ph (4)] and the isothiocyanatotetraoxyphosphorane CH(2)(6-t-Bu-4-Me-C(6)H(2)O)(2)P(NCS)(O(2)C(6)Cl(4)) (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 -NH(2) 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. -NH(2)). The possible rationalization for these results is discussed. Variable-temperature ((1)H, (31)P) 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.

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