Complexes of benzo-15-crown-5 with protonated primary amines and diamines

Olga P. Kryatova; Ivan V. Korendovych; Elena V. Rybak-Akimova

doi:10.1016/j.tet.2004.03.080

Complexes of benzo-15-crown-5 with protonated primary amines and diamines

Olga P. Kryatova, Ivan V. Korendovych, Elena V. Rybak-Akimova

Research output: Contribution to journal › Article

27 Scopus citations

Abstract

Three complexes of benzo-15-crown-5 (B15C5) with protonated primary amines [PhCH₂NH₃(B15C5)](ClO₄), [p-C₆H ₄(CH₂NH₃)₂(B15C5) ₂](ClO₄)₂, and [(CH₂) ₄(NH₃)₂(B15C5)₂](SCN)₂ were isolated and studied in acetonitrile solutions by NMR, and in the solid state by X-ray crystallography. In all complexes, one B15C5 molecule was bound with each R-NH₃⁺ moiety with characteristic small separation of 1.84-1.86Å between the nitrogen of the R-NH₃ ⁺ group and the O₅ mean plane of the crown residue. No sandwich-type complexes with a 1:2 R-NH₃⁺/B15C5 stoichiometry were observed. Binding affinities of B15C5 in acetonitrile were similar for all ammonium cations studied: K₁=550±10 M ^-1 for [PhCH₂NH₃]⁺; K ₁=1100±100 and K₂=400±30 M^-1 for [p-C₆H₄(CH₂NH₃)₂] ²⁺; and K₁=1100±100 and K₂=300±30 M^-1 for [H₃N(CH₂)₄NH ₃]²⁺. The complexation is primarily enthalpy-driven (ΔH°=-4.9±0.5kcal/mol, ΔS°=-3.8±1.0eu for PhCH₂NH₃⁺-B15C5), as determined by variable temperature ¹H NMR titrations.

Original language	English (US)
Pages (from-to)	4579-4588
Number of pages	10
Journal	Tetrahedron
Volume	60
Issue number	21
DOIs	https://doi.org/10.1016/j.tet.2004.03.080
State	Published - May 17 2004
Externally published	Yes

Keywords

Alkylammonium
Crown ethers
Host-guest complexes

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

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Kryatova, O. P., Korendovych, I. V., & Rybak-Akimova, E. V. (2004). Complexes of benzo-15-crown-5 with protonated primary amines and diamines. Tetrahedron, 60(21), 4579-4588. https://doi.org/10.1016/j.tet.2004.03.080

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title = "Complexes of benzo-15-crown-5 with protonated primary amines and diamines",

abstract = "Three complexes of benzo-15-crown-5 (B15C5) with protonated primary amines [PhCH2NH3(B15C5)](ClO4), [p-C6H 4(CH2NH3)2(B15C5) 2](ClO4)2, and [(CH2) 4(NH3)2(B15C5)2](SCN)2 were isolated and studied in acetonitrile solutions by NMR, and in the solid state by X-ray crystallography. In all complexes, one B15C5 molecule was bound with each R-NH3+ moiety with characteristic small separation of 1.84-1.86{\AA} between the nitrogen of the R-NH3 + group and the O5 mean plane of the crown residue. No sandwich-type complexes with a 1:2 R-NH3+/B15C5 stoichiometry were observed. Binding affinities of B15C5 in acetonitrile were similar for all ammonium cations studied: K1=550±10 M -1 for [PhCH2NH3]+; K 1=1100±100 and K2=400±30 M-1 for [p-C6H4(CH2NH3)2] 2+; and K1=1100±100 and K2=300±30 M-1 for [H3N(CH2)4NH 3]2+. The complexation is primarily enthalpy-driven (ΔH°=-4.9±0.5kcal/mol, ΔS°=-3.8±1.0eu for PhCH2NH3+-B15C5), as determined by variable temperature 1H NMR titrations.",

keywords = "Alkylammonium, Crown ethers, Host-guest complexes",

author = "Kryatova, {Olga P.} and Korendovych, {Ivan V.} and Rybak-Akimova, {Elena V.}",

year = "2004",

month = may,

day = "17",

doi = "10.1016/j.tet.2004.03.080",

language = "English (US)",

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pages = "4579--4588",

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TY - JOUR

T1 - Complexes of benzo-15-crown-5 with protonated primary amines and diamines

AU - Kryatova, Olga P.

AU - Korendovych, Ivan V.

AU - Rybak-Akimova, Elena V.

PY - 2004/5/17

Y1 - 2004/5/17

N2 - Three complexes of benzo-15-crown-5 (B15C5) with protonated primary amines [PhCH2NH3(B15C5)](ClO4), [p-C6H 4(CH2NH3)2(B15C5) 2](ClO4)2, and [(CH2) 4(NH3)2(B15C5)2](SCN)2 were isolated and studied in acetonitrile solutions by NMR, and in the solid state by X-ray crystallography. In all complexes, one B15C5 molecule was bound with each R-NH3+ moiety with characteristic small separation of 1.84-1.86Å between the nitrogen of the R-NH3 + group and the O5 mean plane of the crown residue. No sandwich-type complexes with a 1:2 R-NH3+/B15C5 stoichiometry were observed. Binding affinities of B15C5 in acetonitrile were similar for all ammonium cations studied: K1=550±10 M -1 for [PhCH2NH3]+; K 1=1100±100 and K2=400±30 M-1 for [p-C6H4(CH2NH3)2] 2+; and K1=1100±100 and K2=300±30 M-1 for [H3N(CH2)4NH 3]2+. The complexation is primarily enthalpy-driven (ΔH°=-4.9±0.5kcal/mol, ΔS°=-3.8±1.0eu for PhCH2NH3+-B15C5), as determined by variable temperature 1H NMR titrations.

AB - Three complexes of benzo-15-crown-5 (B15C5) with protonated primary amines [PhCH2NH3(B15C5)](ClO4), [p-C6H 4(CH2NH3)2(B15C5) 2](ClO4)2, and [(CH2) 4(NH3)2(B15C5)2](SCN)2 were isolated and studied in acetonitrile solutions by NMR, and in the solid state by X-ray crystallography. In all complexes, one B15C5 molecule was bound with each R-NH3+ moiety with characteristic small separation of 1.84-1.86Å between the nitrogen of the R-NH3 + group and the O5 mean plane of the crown residue. No sandwich-type complexes with a 1:2 R-NH3+/B15C5 stoichiometry were observed. Binding affinities of B15C5 in acetonitrile were similar for all ammonium cations studied: K1=550±10 M -1 for [PhCH2NH3]+; K 1=1100±100 and K2=400±30 M-1 for [p-C6H4(CH2NH3)2] 2+; and K1=1100±100 and K2=300±30 M-1 for [H3N(CH2)4NH 3]2+. The complexation is primarily enthalpy-driven (ΔH°=-4.9±0.5kcal/mol, ΔS°=-3.8±1.0eu for PhCH2NH3+-B15C5), as determined by variable temperature 1H NMR titrations.

KW - Alkylammonium

KW - Crown ethers

KW - Host-guest complexes

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U2 - 10.1016/j.tet.2004.03.080

DO - 10.1016/j.tet.2004.03.080

M3 - Article

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VL - 60

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JO - Tetrahedron

JF - Tetrahedron

SN - 0040-4020

IS - 21

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