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Besli S, Coles SJ, Davies DB, Hursthouse MB, Kilic A, Mayer TA, Shaw RA: Structural investigations of phosphorus-nitrogen compounds. 5. Acta Crystallogr B. 2002 Dec;58(Pt 6):1067-73. Epub 2002 Nov 28.
Relationships between molecular parameters of 2,2-diphenyl-4,6-cis-oxytetra (ethyleneoxy)-4,6-R2-cyclotriphosphazatrienes (R = Cl, OCH2CF3, OPh, OMe, NHPh, NHBut) and substituent basicity constants.. A systematic study of the products of nucleophilic substitution reactions of cis-ansa N (3) P (3) Ph (2)[O (CH (2) CH (2) O)(4)] Cl (2) (3) is reported. These reactions give a number of new structures with the general formula N (3) P (3) Ph (2)[O (CH (2) CH (2) O)(4)] R (2) [where R = OCH (2) CF (3) (4), OPh (5), OMe (6), NHPh (7 x H (2) O), NHBu (t) (8)]. A comparison has been made between the sum of the substituent basicity constants, Sigmaalpha (R), that are obtained in nitrobenzene solution and eight molecular parameters of the N (3) P (3) ring [the P-N bond lengths a, b, c; the internal bond angles alpha, beta, gamma, delta; and the difference between the bond lengths a and b, Delta (P-N)]. It is found that the systematic changes in the molecular parameters of (3)-(8) are in line with changes in alpha (R) values. This result implies the similarity in relative electron-releasing capacity of substituents R in the solid state and in solution. |
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