Phosphorus-nitrogen compounds: Part 15. Synthesis, anisochronism and the relationship between crystallographic and spectral data of monotopic spiro-crypta phosphazenes

Nuran Asmafiliz; Elif Ece İlter; Zeynel Kiliç; Tuncer Hökelek; Ertan Şahes

doi:10.1007/s12039-008-0060-x

Phosphorus-nitrogen compounds: Part 15. Synthesis, anisochronism and the relationship between crystallographic and spectral data of monotopic spiro-crypta phosphazenes

Nuran Asmafiliz
, Elif Ece İlter
, Zeynel Kiliç
, Tuncer Hökelek
, Ertan Şahes

Hacettepe University

Ankara University
Ataturk University

Research output: Contribution to journal › Article › peer-review

21 Citations (Scopus)

Abstract

The reactions of hexachlorocyclotriphosphazatriene, N ₃ P ₃ Cl ₆ , with N ₂ O ₂ -donor type coronands, Ph2[OR ₁ O][CH ₂ NHR ₂ NHCH ₂ ] [R ₁ = (CH ₂ ) ₃ , R ₂ = (CH ₂ ) ₃ (1), R ₁ = (CH ₂ ) ₃ , R ₂ = (CH ₂ ) ₄ (2), R ₁ = (CH ₂ ) ₄ , R ₂ = (CH ₂ ) ₄ (3)], give monotopic spiro-crypta phosphazene architectures, N ₃ P ₃ Cl ₄ {Ph ₂ [OR ₁ O][CH ₂ NR ₂ NCH ₂ ]) [R ₁ = (CH ₂ ) ₃ , R ₂ = (CH ₂ ) ₃ (4), R ₁ = (CH ₂ ) ₃ , R ₂ = (CH ₂ ) ₄ (5) and R ₁ = (CH ₂ ) ₄ , R ₂ = (CH ₂ ) ₄ (6)], respectively. The reaction of 4 with excess pyrrolidine leads to the formation of geminal N ₃ P ₃ Cl ₂ (C ₅ H ₅ N) ₂ {Ph ₂ [O(CH ₂ ) ₃ O] [CH ₂ N(CH ₂ ) ₃ NCH ₂ ]} (7). The ³¹ P-NMR spectra of 5 and 6 indicate that these compounds have anisochronism. The structures of 5, 6 and 7 were investigated by X-ray crystallography. For 7, the sums of the bond angles around the N atoms were 348·6(2)° and 349·7(2)° indicating that the N atoms have pyramidal configurations and are stereogenic. The relationship between the chemical shift values δP _(spiro) and the Δ(P-N) (electron density transfer parameters) of 4, 5, 6, 7 and the analogous compounds as well as the relationship between the Δ(δP) values and the above mentioned Δ(P-N) are presented respectively. In addition, the relationship between the endocyclic NPN bond angles of these compounds and the ³¹ P-NMR chemical shifts of the spiro-phosphorus atoms were investigated. The spectroscopic and structural investigations of the compounds were made by elemental analyses, MS, FTIR, one-dimensional ¹ H-, ¹³ C-, ³¹ P-NMR, DEPT and two-dimensional COSY, HETCOR, HMBC, homo- and heteronuclear correlation techniques.

Original language	English
Pages (from-to)	363-376
Number of pages	14
Journal	Journal of Chemical Sciences
Volume	120
Issue number	4
DOIs	https://doi.org/10.1007/s12039-008-0060-x
Publication status	Published - Jul 2008

Keywords

Anisochrony
Spectroscopy
Spiro-crypta-phosphazenes
Synthesis

Access to Document

10.1007/s12039-008-0060-x

Cite this

@article{e128aa08a43e469f86942dbae4dd0a27,

title = "Phosphorus-nitrogen compounds: Part 15. Synthesis, anisochronism and the relationship between crystallographic and spectral data of monotopic spiro-crypta phosphazenes",

abstract = " The reactions of hexachlorocyclotriphosphazatriene, N 3 P 3 Cl 6 , with N 2 O 2 -donor type coronands, Ph2[OR 1 O][CH 2 NHR 2 NHCH 2 ] [R 1 = (CH 2 ) 3 , R 2 = (CH 2 ) 3 (1), R 1 = (CH 2 ) 3 , R 2 = (CH 2 ) 4 (2), R 1 = (CH 2 ) 4 , R 2 = (CH 2 ) 4 (3)], give monotopic spiro-crypta phosphazene architectures, N 3 P 3 Cl 4 \{Ph 2 [OR 1 O][CH 2 NR 2 NCH 2 ]) [R 1 = (CH 2 ) 3 , R 2 = (CH 2 ) 3 (4), R 1 = (CH 2 ) 3 , R 2 = (CH 2 ) 4 (5) and R 1 = (CH 2 ) 4 , R 2 = (CH 2 ) 4 (6)], respectively. The reaction of 4 with excess pyrrolidine leads to the formation of geminal N 3 P 3 Cl 2 (C 5 H 5 N) 2 \{Ph 2 [O(CH 2 ) 3 O] [CH 2 N(CH 2 ) 3 NCH 2 ]\} (7). The 31 P-NMR spectra of 5 and 6 indicate that these compounds have anisochronism. The structures of 5, 6 and 7 were investigated by X-ray crystallography. For 7, the sums of the bond angles around the N atoms were 348·6(2)° and 349·7(2)° indicating that the N atoms have pyramidal configurations and are stereogenic. The relationship between the chemical shift values δP (spiro) and the Δ(P-N) (electron density transfer parameters) of 4, 5, 6, 7 and the analogous compounds as well as the relationship between the Δ(δP) values and the above mentioned Δ(P-N) are presented respectively. In addition, the relationship between the endocyclic NPN bond angles of these compounds and the 31 P-NMR chemical shifts of the spiro-phosphorus atoms were investigated. The spectroscopic and structural investigations of the compounds were made by elemental analyses, MS, FTIR, one-dimensional 1 H-, 13 C-, 31 P-NMR, DEPT and two-dimensional COSY, HETCOR, HMBC, homo- and heteronuclear correlation techniques.",

keywords = "Anisochrony, Spectroscopy, Spiro-crypta-phosphazenes, Synthesis",

author = "Nuran Asmafiliz and İlter, \{Elif Ece\} and Zeynel Kili{\c c} and Tuncer H{\"o}kelek and Ertan {\c S}ahes",

year = "2008",

month = jul,

doi = "10.1007/s12039-008-0060-x",

language = "English",

volume = "120",

pages = "363--376",

journal = "Journal of Chemical Sciences",

issn = "0974-3626",

publisher = "Springer India",

number = "4",

}

TY - JOUR

T1 - Phosphorus-nitrogen compounds

T2 - Part 15. Synthesis, anisochronism and the relationship between crystallographic and spectral data of monotopic spiro-crypta phosphazenes

AU - Asmafiliz, Nuran

AU - İlter, Elif Ece

AU - Kiliç, Zeynel

AU - Hökelek, Tuncer

AU - Şahes, Ertan

PY - 2008/7

Y1 - 2008/7

N2 - The reactions of hexachlorocyclotriphosphazatriene, N 3 P 3 Cl 6 , with N 2 O 2 -donor type coronands, Ph2[OR 1 O][CH 2 NHR 2 NHCH 2 ] [R 1 = (CH 2 ) 3 , R 2 = (CH 2 ) 3 (1), R 1 = (CH 2 ) 3 , R 2 = (CH 2 ) 4 (2), R 1 = (CH 2 ) 4 , R 2 = (CH 2 ) 4 (3)], give monotopic spiro-crypta phosphazene architectures, N 3 P 3 Cl 4 {Ph 2 [OR 1 O][CH 2 NR 2 NCH 2 ]) [R 1 = (CH 2 ) 3 , R 2 = (CH 2 ) 3 (4), R 1 = (CH 2 ) 3 , R 2 = (CH 2 ) 4 (5) and R 1 = (CH 2 ) 4 , R 2 = (CH 2 ) 4 (6)], respectively. The reaction of 4 with excess pyrrolidine leads to the formation of geminal N 3 P 3 Cl 2 (C 5 H 5 N) 2 {Ph 2 [O(CH 2 ) 3 O] [CH 2 N(CH 2 ) 3 NCH 2 ]} (7). The 31 P-NMR spectra of 5 and 6 indicate that these compounds have anisochronism. The structures of 5, 6 and 7 were investigated by X-ray crystallography. For 7, the sums of the bond angles around the N atoms were 348·6(2)° and 349·7(2)° indicating that the N atoms have pyramidal configurations and are stereogenic. The relationship between the chemical shift values δP (spiro) and the Δ(P-N) (electron density transfer parameters) of 4, 5, 6, 7 and the analogous compounds as well as the relationship between the Δ(δP) values and the above mentioned Δ(P-N) are presented respectively. In addition, the relationship between the endocyclic NPN bond angles of these compounds and the 31 P-NMR chemical shifts of the spiro-phosphorus atoms were investigated. The spectroscopic and structural investigations of the compounds were made by elemental analyses, MS, FTIR, one-dimensional 1 H-, 13 C-, 31 P-NMR, DEPT and two-dimensional COSY, HETCOR, HMBC, homo- and heteronuclear correlation techniques.

AB - The reactions of hexachlorocyclotriphosphazatriene, N 3 P 3 Cl 6 , with N 2 O 2 -donor type coronands, Ph2[OR 1 O][CH 2 NHR 2 NHCH 2 ] [R 1 = (CH 2 ) 3 , R 2 = (CH 2 ) 3 (1), R 1 = (CH 2 ) 3 , R 2 = (CH 2 ) 4 (2), R 1 = (CH 2 ) 4 , R 2 = (CH 2 ) 4 (3)], give monotopic spiro-crypta phosphazene architectures, N 3 P 3 Cl 4 {Ph 2 [OR 1 O][CH 2 NR 2 NCH 2 ]) [R 1 = (CH 2 ) 3 , R 2 = (CH 2 ) 3 (4), R 1 = (CH 2 ) 3 , R 2 = (CH 2 ) 4 (5) and R 1 = (CH 2 ) 4 , R 2 = (CH 2 ) 4 (6)], respectively. The reaction of 4 with excess pyrrolidine leads to the formation of geminal N 3 P 3 Cl 2 (C 5 H 5 N) 2 {Ph 2 [O(CH 2 ) 3 O] [CH 2 N(CH 2 ) 3 NCH 2 ]} (7). The 31 P-NMR spectra of 5 and 6 indicate that these compounds have anisochronism. The structures of 5, 6 and 7 were investigated by X-ray crystallography. For 7, the sums of the bond angles around the N atoms were 348·6(2)° and 349·7(2)° indicating that the N atoms have pyramidal configurations and are stereogenic. The relationship between the chemical shift values δP (spiro) and the Δ(P-N) (electron density transfer parameters) of 4, 5, 6, 7 and the analogous compounds as well as the relationship between the Δ(δP) values and the above mentioned Δ(P-N) are presented respectively. In addition, the relationship between the endocyclic NPN bond angles of these compounds and the 31 P-NMR chemical shifts of the spiro-phosphorus atoms were investigated. The spectroscopic and structural investigations of the compounds were made by elemental analyses, MS, FTIR, one-dimensional 1 H-, 13 C-, 31 P-NMR, DEPT and two-dimensional COSY, HETCOR, HMBC, homo- and heteronuclear correlation techniques.

KW - Anisochrony

KW - Spectroscopy

KW - Spiro-crypta-phosphazenes

KW - Synthesis

UR - https://www.scopus.com/pages/publications/49449086806

U2 - 10.1007/s12039-008-0060-x

DO - 10.1007/s12039-008-0060-x

M3 - Article

AN - SCOPUS:49449086806

SN - 0974-3626

VL - 120

SP - 363

EP - 376

JO - Journal of Chemical Sciences

JF - Journal of Chemical Sciences

IS - 4

ER -

Phosphorus-nitrogen compounds: Part 15. Synthesis, anisochronism and the relationship between crystallographic and spectral data of monotopic spiro-crypta phosphazenes

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Cite this