Mechanisms of formation and dissociation of a cesium-calix[4]arene acetamide complex in solution: A Cs-133 dynamic NMR study

被引：17

作者：

Meier, UC ^{[1
]}

Detellier, C ^{[1
]}

机构：

[1] Univ Ottawa, Ottawa Carleton Chem Inst, Ottawa, ON K1N 6N5, Canada

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 1999年 / 103卷 / 20期

关键词：

D O I：

10.1021/jp9843609

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The kinetics and mechanism of the cesium cation complexation by 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(N,N-diaethylaminocarbonyl)methoxy calix[4]arene (1) were studied in a binary mixture (1:1 by volume) of deuterated acetonitrile and deuterated chloroform using H-1 and Cs-133 NMR spectroscopy. The formation of cone complexes with 1:1 and 2:1 Cs+/1 stoichiometries is reported. The complex formation of the 1:1 complex is quantitative (K-f > 10(4) M-1), and the equilibrium constant for the 2:1 complex is 3 +/- 2 M-1 at 238 K. The first complexed Cs+ is embedded in the cavity made of the four phenolic and four carbonyl oxygens, whereas it is suggested that the second Cs+ is loosely bound by the amido groups. The second Cs+ and the solvated Cs+ are in fast exchange. The embedded Cs+ is in slow exchange with solvated Cs+. The decomplexation process of the 1:1 complex follows a unimolecular dissociation mechanism. It is characterized by Delta H* = 67 +/- 2 kJ/mol and Delta S* = 40 +/- 3 J/(mol K). An intramolecular exchange between the two bound cesium cations is not observed.

引用

页码：3825 / 3829

页数：5

共 31 条

[21] H-1, LI-7, NA-23, CS-133 NMR-STUDY ON THE COMPLEX PROPERTIES OF AZAMACROCYCLIC ETHER-BISLACTONES AND AMINE-BISLACTAM [J].

ZHANG, AJ ;

WANG, SM ;

QIN, SY .

ACTA CHIMICA SINICA, 1991, 49 (02) :164-169

[22] H-1, LI-7 AND CS-133 MULTICOMPONENT SELF-DIFFUSION NMR-STUDY OF ION BINDING OF LI+ AND CS+ TO NUCLEOTIDES AND AGGREGATION OF NUCLEOTIDES IN AQUEOUS-SOLUTION [J].

STOKKELAND, I ;

STILBS, P .

BIOPHYSICAL CHEMISTRY, 1986, 24 (01) :61-69

[23] 1H and 7Li NMR study on the complex formation of lithium cations with pyridinium derivatives of calix[4]arenes [J].

Mohammed-Ziegler, I ;

Szöllösy, A ;

Kubinyi, M ;

Grofcsik, A ;

Grün, A ;

Bitter, I .

SUPRAMOLECULAR CHEMISTRY, 2004, 16 (06) :415-421

[24] NMR-STUDIES ON [RH(ETA-6-ARENE)(P(OPH)3)2]CLO4 IN THE PRESENCE OF ACETONE-D6 ARENE DISSOCIATION AND DYNAMIC BEHAVIOR OF THE SOLVENT COMPLEX [J].

BITTERSMANN, E ;

HILDENBRAND, K ;

CERVILLA, A ;

LAHUERTA, P .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1985, 287 (02) :255-263

[25] Conformational dynamics of 5,11,17,23,-tetra-p-tert-butyl-25,27-di(N,N-diethylaminocarbonyl)methoxy-26,28-dimethoxycalix[4]arene and its kinetics and mechanisms of the cesium cation complexation in solution studied by 1H, 13C, and 133Cs NMR spectroscopy [J].

Meier, UC ;

Detellier, C .

JOURNAL OF PHYSICAL CHEMISTRY A, 1999, 103 (46) :9204-9210

[26] 1,3-calix[4]-bis-crown-6. Cesium complexation studies by Cs-133- and H-1-NMR spectroscopy. Evidence for mononuclear and binuclear complexes from X-ray diffraction. Modeling of the metal complexation [J].

Asfari, Z ;

Naumann, C ;

Vicens, J ;

Nierlich, M ;

Thuery, P ;

Bressot, C ;

Lamare, V ;

Dozol, JF .

NEW JOURNAL OF CHEMISTRY, 1996, 20 (11) :1183-1194

[27] THE SOLUTION CHEMISTRY OF ORGANOTIN COMPOUNDS .1. A H-1-NMR STUDY OF THE COMPLEX-FORMATION BETWEEN METHYLTIN TRICHLORIDE AND 4-SUBSTITUTED PYRIDINES [J].

FUJIWARA, H ;

SAKAI, F ;

TAKEYAMA, M ;

SASAKI, Y .

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 1981, 54 (05) :1380-1384

[28] Effect of Diluents on The Synergistic Solvent Extraction and Separation of Trivalent Lanthanoids With 4-Benzoyl-3-Phenyl-5-Isoxazolone and tert-Butylcalix[4]Arene Tetrakis(N,N-Dimethyl Acetamide) and Structural Study of Gd(III) Solid Complex By IR and NMR [J].

Petrova, Maria A. ;

Lachkova, Victoria I. ;

Vassilev, Nikolay G. ;

Varbanov, Sabi G. .

INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 2010, 49 (13) :6189-6195

[29] H-1-NMR STUDY ON THE COMPLEX-FORMATION OF CO(II) WITH CROWN ETHER [12]CROWN-4 IN CD3NO2-CH3OH MIXTURES - THERMODYNAMICS AND SOLVENT ASSISTED DISSOCIATION [J].

DICKERT, FL ;

GUMBRECHT, W .

ZEITSCHRIFT FUR PHYSIKALISCHE CHEMIE NEUE FOLGE, 1984, 141 :169-176

[30] Single-crystal X-ray diffraction study, NMR and electrochemical analysis of a copper(i) 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis-[(6-methyl-2,2′-bipyridyl-6-yl)methoxy]calix[4]arene complex: an original M4L2 "hand-to-hand" system [J].

Regnouf-de-Vains, J-B ;

Malaman, B. ;

Bouguet-Bonnet, S. ;

Poinsignon, Sophie ;

Leclerc, Sebastien ;

Beley, M. .

NEW JOURNAL OF CHEMISTRY, 2019, 43 (33) :13282-13293

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