Solid-state structural chemistry of lariat ether and BiBLE cation complexes: metal-ion identity and coordination number determine cavity size

Gandour, Richard D.; Fronczek, Frank R.; Gatto, Vincent J.; Minganti, Carlo; Schultz, Rose Ann; White, Brandyn; Arnold, Kristin A.; MAZZOCCHI, D.; Miller, Steven R.; Gokel, George W.

doi:10.1021/ja00274a037

Cited by 116 publications

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“…Water on one face of the macrocycle and the carboxylate and carboxyls on the other face encapsulate the cations. These complexes resemble bibracchial lariat ether and cryptand complexes (12). Table 3 summarizes the coordination about each cation.…”

Section: Comparison Of 18c6a6 Complexesmentioning

confidence: 99%

“…Both ligands are multi-armed lariat ethers, and we follow an earlier analysis of the solid-state smctures of neutral lariat ether complexes (12). For each complex, we calculate the mean cavity radius by the procedure of Mathieu et al, which averages the differences between the metal-donor distance and the covalent radius of the donor atom for all donors in the ligand (13).…”

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confidence: 99%

“…We describe the detailed reorganizations that the different guest ions provoke in the host and the ways in which those reorganizations may be discerned. We use skeletal drawings, which include only the donor atoms of the ligands (12),-to reveal the topographies of the donor atoms about the guest cations. We next present the 18 torsion angles of a macrocycle on a polar-coordinate map (16 formations of many 18-crown-6 metal cation complexes (1 8).…”

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confidence: 99%

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Solid-state chemistry of polycarboxylate crown ether cation complexes: cooperative binding of water and metal ions by flexible chorands

Dutton¹,

Fyles²,

Suresh³

et al. 1993

Can. J. Chem.

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The solid-state structures of alkali-metal salt complexes of crown ether tetra-and hexa-carboxylic acids (18C6A4 and 18C6A6) have been determined. The sodium salt of 18C6A6 crystallizes as the trihydrate in orthorhombic space group P2,2,2, (a = 7.6868(12), b = 15.429(3), c = 21.975(2) A, R = 0.031 for 5192 observed data); the potassium salt of 18C6A6 crystallizes as the the trihydrate in orthorhombic space group P2,2,2, (a = 7.671 1(8), b = 15.709(2), c = 21.966(5) A, R = 0.035 for 2521 observed data); the thallium(1) salt of 18C6A6~rystallizes as the dihydrate in orthorhombic space group P2,2,2, (a = 12.0331(10), b = 12.4333(12), c = 17.366(2) A, R = 0.035 for 4952 observed data); and the cesium salt of 18C6& crystallizes as the dihydrate in monoclinic space group P2, (a = 7.708(3), b = 13.492(2), c = 11.9501(9) A, P = 94.49(2)", R = 0.029 for 4480 observed data). The sodium salt of 18S6A4 crystallizes as the dihydrate in monoclinic space group P2, (a = 11.4368(1 I), b = 7.7068(1 l), c = 12.6579(12) A, P = 98.515(8)", R = 0.035 for 3000 observed data); the thallium(1) salt ofo18C6A4 crystallizes as the dihydrate in monoclinic space group P2,(a = 11.719(2), b = 7.668(2), c = 12.8403(13) A, P = 99.052(9)", R = 0.040 for 3981 observed data); and the cesium saltoof 18C6A4 crystallizes as the dihydrate in monoclinic space group P2, (a = 11.787(2), b = 7.637(2), c = 13.001(2) A, p = 98.705(12)", R = 0.038 for 3428 observed data). Both chorands exhibit a cooperative relationship of mean cavity radius and guest-ion radius, which closely follows the effective ionic radii of the guests. The hexaacid is a preorganized host for monohydrated cations. It provides a trigonal hydrogen bonding receptor site for the water molecule, and up to nine oxygen donors for cation binding. Guests ranging in size from ~a ' to CS' are accommodated without distortion of the macrocyclic framework. The tetraacid is similarly tolerant of a range of guests, but greater structural reorganization of the ligand is required to optimize contacts with fully dehydrated cations. Skeletal drawings of donor atoms, in conjunction with polar coordinate maps of torsion angles, reveal how the demands of the guest are accommodated by the host. (2) A, p = 98,705(12)" et R = 0,038 pour 3428 donnees observees. Les deux chorands presentent une relation cooperative des rayons moyens de cavite et d'ion invite qui suit de trks prks celle des rayons ioniques effectifs des invites. L'hexaacide est un hBte preorganise pour les cations monohydrates. I1 fournit aux molCcules d'eau un site recepteur pour une liaison hydrogkne trigonale et jusqu'a neuf oxygenes donneurs pour des liaisons avec les cations. Les invites dont la taille se situe entre celles du Na' et du Cs+ s'accommodent sans distorsions dans la structure macrocyclique. Le tetraacide tolere aussi une grande variCtC d'invites; toutefois, une plus grande reorganisation structurale est requise du ligand pour optimiser les contacts avec les cations complktement deshydrates. Des diagrammes du squelette des atomes d...

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Section: Comparison Of 18c6a6 Complexesmentioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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Solid-state chemistry of polycarboxylate crown ether cation complexes: cooperative binding of water and metal ions by flexible chorands

Dutton¹,

Fyles²,

Suresh³

et al. 1993

Can. J. Chem.

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“…The interrelationship of the number of donors (with their topology) and the effective ionic radius of the bound cation governs binding in flexible neutral ligands (15). The same applies to flexible charged ligands, with the additional complexity that ligand flexibility decreases as charge increases.…”

Section: Determination Of Complexation Constantsmentioning

confidence: 99%

“…The carboxylates could act as additional ligating sites in a fashion similar to the neutral donor arms of lariat ethers (15,16). Evidence from infrared and nuclear magnetic resonance spectroscopy (12), from electron spin resonance spectroscopy (1 I), and from analysis of stability constant data (12,17) suggests that direct and cooperative carboxylate-cation interactions occur, especially with small cations in solvents of moderate polarity.…”

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Synthesis and metal ion complexation behavior of polycarboxylate 18-crown-6 ethers derived from tartaric acid

Dutton¹,

Fyles²,

McDermid³

1988

Can. J. Chem.

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. Can. J. Chem. 66, 1097 (1988). The metal ion complexation behavior of four 18-crown-6 ethers derived from (+)-and meso-tartaric acid is examined. Preparations of a meso-crown ether diacid and of a crown ether hexacid from three units of (+)-tartaric acid are described. Acidity constants and stability constants for complexation of metal cations in aqueous solution were determined by potentiometric titration. The complexes are substantially stabilized by favourable electrostatic interactions and are of similar stability to complexes of cryptands and EDTA. The complexation behavior of the series can be rationalized in terms of electrostatic interactions, direct coordination of the cations by at least one carboxylate from the crown ether periphery, and rigidification of the ligands as the anionic charge increases. Distributions of charge influence the relative stability of isomeric complexes. Highly charged polycarboxylate crown ethers are effective, but relatively unselective, cation complexing agents for a range of cations. The complexes are stable to pH 3 and the ligands can be used as simultaneous pH and metal ion buffers. The underlying theme in the complexation chemistry of 18C6 prefer an ideal D3d symmetry (1 8). Thus, both RR1 8C6A2 macrocycles, is the control of complex formation by control of and 18C6A4 are incapable of symmetrically interacting with a ligand structure through synthesis ( l , 2 ) . From this perspective, bound cation, either by direct contact or by indirect coulombic crown ethers derived from (+)-tartaric acid possess a number of attraction without some distortions of the macrocycle from appealing features as frameworks for the construction of specific complexing agents. Firstly, the carboxyl groups provide an easy synthetic entry to a wide range of derivatives (3-7). Secondly, the tartaric acid units show a strong conformational preference for an anti disposition of the carboxylates and other carboxylate derived groups (8-12). This limits overall conformational flexibility (8,11,12) and leads to well-defined conformations in which the carboxylate derived groups lie axial to the plane of the macrocycle (8-12). Lateral interactions between substituent groups and bound substrates are thus favored (3,4,13,14). Finally, the presence of charged groups on the macrocyclic periphery leads to markedly enhanced cation complexation relative to uncharged ligands of similar structure (3,8,12). This is primarily a result of a favorable electrostatic interaction between the anionic ligand and the complexed cation (5,8).Additional effects may be important. The carboxylates could act as additional ligating sites in a fashion similar to the neutral donor arms of lariat ethers (15,16). Evidence from infrared and nuclear magnetic resonance spectroscopy (12), from electron spin resonance spectroscopy (1 I), and from analysis of stability constant data (12,17) suggests that direct and cooperative carboxylate-cation interactions occur, especially with small cations in solvents of moderate polarity. Such contac...

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Experimental Evidence for Alkali Metal Cation−π Interactions

2000

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Solid-state structural chemistry of lariat ether and BiBLE cation complexes: metal-ion identity and coordination number determine cavity size

Cited by 116 publications

References 4 publications

Solid-state chemistry of polycarboxylate crown ether cation complexes: cooperative binding of water and metal ions by flexible chorands

Solid-state chemistry of polycarboxylate crown ether cation complexes: cooperative binding of water and metal ions by flexible chorands

Synthesis and metal ion complexation behavior of polycarboxylate 18-crown-6 ethers derived from tartaric acid

Experimental Evidence for Alkali Metal Cation−π Interactions

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