Cryptand

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Structure of [2.2.2]cryptand encapsulating a potassium cation (purple). At crystalline state, obtained with an X-ray diffraction. Cryptate of potassium cation.jpg
Structure of [2.2.2]cryptand encapsulating a potassium cation (purple). At crystalline state, obtained with an X-ray diffraction.
[2.2.2]Cryptand Cryptand.svg
[2.2.2]Cryptand

In chemistry, cryptands are a family of synthetic, bicyclic and polycyclic, multidentate ligands for a variety of cations. [2] The Nobel Prize for Chemistry in 1987 was given to Donald J. Cram, Jean-Marie Lehn, and Charles J. Pedersen for their efforts in discovering and determining uses of cryptands and crown ethers, thus launching the now flourishing field of supramolecular chemistry. [3] The term cryptand implies that this ligand binds substrates in a crypt, interring the guest as in a burial. These molecules are three-dimensional analogues of crown ethers but are more selective and strong as complexes for the guest ions. The resulting complexes are lipophilic. [4]

Contents

Structure

The most common and most important cryptand is N[CH2CH2OCH2CH2OCH2CH2]3N; the systematic IUPAC name for this compound is 1,10-diaza-4,7,13,16,21,24-hexaoxabicyclo[8.8.8]hexacosane. This compound is termed [2.2.2]cryptand, where the numbers indicate the number of ether oxygen atoms (and hence binding sites) in each of the three bridges between the amine nitrogen caps. Many cryptands are commercially available under the tradename Kryptofix. [5] All-amine cryptands exhibit particularly high affinity for alkali metal cations, which has allowed the isolation of salts of K−. [6]

Properties

Cation binding

The three-dimensional interior cavity of a cryptand provides a binding site – or host – for "guest" ions. The complex between the cationic guest and the cryptand is called a cryptate. Cryptands form complexes with many "hard cations" including NH+
4, lanthanoids, alkali metals, and alkaline earth metals. In contrast to crown ethers, cryptands bind the guest ions using both nitrogen and oxygen donors. This three-dimensional encapsulation mode confers some size-selectivity, enabling discrimination among alkali metal cations (e.g. Na+ vs. K+). Some cryptands are luminescent. [7]

Anion binding

Polyamine-based cryptands can be converted to polyammonium cages, which exhibit high affinities for anions. [8]

Laboratory uses

Cryptands enjoy some commercial applications (e.g. in homogenous-time-resolved-fluorescence, HTRF, technologies using Eu3+ as central ion). More importantly, they are reagents for the synthesis of inorganic and organometallic salts. Although more expensive and more difficult to prepare than crown ethers, cryptands bind alkali metals more strongly. [9] They are especially used to isolate salts of highly basic anions. [10] They convert solvated alkali metal cations into lipophilic cations, thereby conferring solubility in organic solvents to the resulting salts.

Referring to achievements that have been recognized in textbooks, cryptands enabled the synthesis of the alkalides and electrides. For example, addition of 2,2,2-cryptand to a solution of sodium in ammonia affords the salt [Na(2,2,2-crypt)]+e−, isolated a blue-black paramagnetic solid. [11] [12] Cryptands have also been used in the crystallization of Zintl ions such as Sn4−
9. [13]

Although rarely practical, cryptands can serve as phase transfer catalysts since their cationic complexes are lipophilic. [14]

See also

Related Research Articles

<span class="mw-page-title-main">Alkali metal</span> Group of highly reactive chemical elements

The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), and francium (Fr). Together with hydrogen they constitute group 1, which lies in the s-block of the periodic table. All alkali metals have their outermost electron in an s-orbital: this shared electron configuration results in their having very similar characteristic properties. Indeed, the alkali metals provide the best example of group trends in properties in the periodic table, with elements exhibiting well-characterised homologous behaviour. This family of elements is also known as the lithium family after its leading element.

Supramolecular chemistry refers to the branch of chemistry concerning chemical systems composed of a discrete number of molecules. The strength of the forces responsible for spatial organization of the system range from weak intermolecular forces, electrostatic charge, or hydrogen bonding to strong covalent bonding, provided that the electronic coupling strength remains small relative to the energy parameters of the component. While traditional chemistry concentrates on the covalent bond, supramolecular chemistry examines the weaker and reversible non-covalent interactions between molecules. These forces include hydrogen bonding, metal coordination, hydrophobic forces, van der Waals forces, pi–pi interactions and electrostatic effects.

<span class="mw-page-title-main">Crown ether</span> Ring molecules with several ether (–O–) groups

In organic chemistry, crown ethers are cyclic chemical compounds that consist of a ring containing several ether groups (R−O−R’). The most common crown ethers are cyclic oligomers of ethylene oxide, the repeating unit being ethyleneoxy, i.e., −CH2CH2O−. Important members of this series are the tetramer (n = 4), the pentamer (n = 5), and the hexamer (n = 6). The term "crown" refers to the resemblance between the structure of a crown ether bound to a cation, and a crown sitting on a person's head. The first number in a crown ether's name refers to the number of atoms in the cycle, and the second number refers to the number of those atoms that are oxygen. Crown ethers are much broader than the oligomers of ethylene oxide; an important group are derived from catechol.

Anions that interact weakly with cations are termed non-coordinating anions, although a more accurate term is weakly coordinating anion. Non-coordinating anions are useful in studying the reactivity of electrophilic cations. They are commonly found as counterions for cationic metal complexes with an unsaturated coordination sphere. These special anions are essential components of homogeneous alkene polymerisation catalysts, where the active catalyst is a coordinatively unsaturated, cationic transition metal complex. For example, they are employed as counterions for the 14 valence electron cations [(C5H5)2ZrR]+ (R = methyl or a growing polyethylene chain). Complexes derived from non-coordinating anions have been used to catalyze hydrogenation, hydrosilylation, oligomerization, and the living polymerization of alkenes. The popularization of non-coordinating anions has contributed to increased understanding of agostic complexes wherein hydrocarbons and hydrogen serve as ligands. Non-coordinating anions are important components of many superacids, which result from the combination of Brønsted acids and Lewis acids.

<span class="mw-page-title-main">Radical anion</span> Free radical species

In organic chemistry, a radical anion is a free radical species that carries a negative charge. Radical anions are encountered in organic chemistry as reduced derivatives of polycyclic aromatic compounds, e.g. sodium naphthenide. An example of a non-carbon radical anion is the superoxide anion, formed by transfer of one electron to an oxygen molecule. Radical anions are typically indicated by .

<span class="mw-page-title-main">Counterion</span> Ion which negates another oppositely-charged ion in an ionic molecule

In chemistry, a counterion is the ion that accompanies an ionic species in order to maintain electric neutrality. In table salt the sodium ion is the counterion for the chloride ion and vice versa.

In chemistry, a phase-transfer catalyst or PTC is a catalyst that facilitates the transition of a reactant from one phase into another phase where reaction occurs. Phase-transfer catalysis is a special form of catalysis and can act through homogeneous catalysis or heterogeneous catalysis methods depending on the catalyst used. Ionic reactants are often soluble in an aqueous phase but insoluble in an organic phase in the absence of the phase-transfer catalyst. The catalyst functions like a detergent for solubilizing the salts into the organic phase. Phase-transfer catalysis refers to the acceleration of the reaction upon the addition of the phase-transfer catalyst.

<span class="mw-page-title-main">18-Crown-6</span> Chemical compound

18-Crown-6 is an organic compound with the formula [C2H4O]6 and the IUPAC name of 1,4,7,10,13,16-hexaoxacyclooctadecane. It is a white, hygroscopic crystalline solid with a low melting point. Like other crown ethers, 18-crown-6 functions as a ligand for some metal cations with a particular affinity for potassium cations (binding constant in methanol: 106 M−1). The point group of 18-crown-6 is S6. The dipole moment of 18-crown-6 varies in different solvent and under different temperature. Under 25 °C, the dipole moment of 18-crown-6 is 2.76 ± 0.06 D in cyclohexane and 2.73 ± 0.02 in benzene. The synthesis of the crown ethers led to the awarding of the Nobel Prize in Chemistry to Charles J. Pedersen.

<span class="mw-page-title-main">Arenium ion</span> Forms during electrophilic substitution on benzene ring

An arenium ion in organic chemistry is a cyclohexadienyl cation that appears as a reactive intermediate in electrophilic aromatic substitution. For historic reasons this complex is also called a Wheland intermediate, after American chemist George Willard Wheland (1907–1976). They are also called sigma complexes. The smallest arenium ion is the benzenium ion, which is protonated benzene.

<span class="mw-page-title-main">Tetrafluoroborate</span> Anion

Tetrafluoroborate is the anion BF−
4. This tetrahedral species is isoelectronic with tetrafluoroberyllate (BeF2−
4), tetrafluoromethane (CF4), and tetrafluoroammonium (NF+
4) and is valence isoelectronic with many stable and important species including the perchlorate anion, ClO−
4, which is used in similar ways in the laboratory. It arises by the reaction of fluoride salts with the Lewis acid BF3, treatment of tetrafluoroboric acid with base, or by treatment of boric acid with hydrofluoric acid.

<span class="mw-page-title-main">Electride</span> Ionic compound with electrons as the anion

An electride is an ionic compound in which an electron serves the role of the anion. Solutions of alkali metals in ammonia are electride salts. In the case of sodium, these blue solutions consist of [Na(NH3)6]+ and solvated electrons:

A solvated electron is a free electron in a solution, in which it behaves like an anion. An electron's being solvated in a solution means it is bound by the solution. The notation for a solvated electron in formulas of chemical reactions is "e−". Often, discussions of solvated electrons focus on their solutions in ammonia, which are stable for days, but solvated electrons also occur in water and many other solvents – in fact, in any solvent that mediates outer-sphere electron transfer. The solvated electron is responsible for a great deal of radiation chemistry.

Sodium atoms have 11 electrons, one more than the stable configuration of the noble gas neon. As a result, sodium usually forms ionic compounds involving the Na+ cation. Sodium is a reactive alkali metal and is much more stable in ionic compounds. It can also form intermetallic compounds and organosodium compounds. Sodium compounds are often soluble in water.

An alkalide is a chemical compound in which alkali metal atoms are anions with a charge or oxidation state of −1. Until the first discovery of alkalides in the 1970s, alkali metals were known to appear in salts only as cations with a charge or oxidation state of +1. These types of compounds are of theoretical interest due to their unusual stoichiometry and low ionization potentials. Alkalide compounds are chemically related to the electrides, salts in which trapped electrons are effectively the anions.

<span class="mw-page-title-main">Hexafluorophosphate</span> Anion with the chemical formula PF6–

Hexafluorophosphate is an anion with chemical formula of [PF6]−. It is an octahedral species that imparts no color to its salts. [PF6]− is isoelectronic with sulfur hexafluoride, SF6, and the hexafluorosilicate dianion, [SiF6]2−, and hexafluoroantimonate [SbF6]−. In this anion, phosphorus has a valence of 5. Being poorly nucleophilic, hexafluorophosphate is classified as a non-coordinating anion.

<span class="mw-page-title-main">2.2.2-Cryptand</span> Chemical compound

[2.2.2]Cryptand is the organic compound with the formula N(CH2CH2OCH2CH2OCH2CH2)3N. This bicyclic molecule is the most studied member of the cryptand family of chelating agents. It is a white solid. Many analogous compounds are known. Their high affinity for alkali metal cations illustrates the advantages of "preorganization", a concept within the area of supramolecular chemistry.

<span class="mw-page-title-main">Tetrakis(3,5-bis(trifluoromethyl)phenyl)borate</span> Chemical compound

Tetrakis[3,5-bis(trifluoromethyl)phenyl]borate is an anion with chemical formula [{3,5-(CF3)2C6H3}4B]−, which is commonly abbreviated as [BArF4]−, indicating the presence of fluorinated aryl (ArF) groups. It is sometimes referred to as Kobayashi's anion in honour of Hiroshi Kobayashi who led the team that first synthesised it. More commonly it is affectionately nicknamed "BARF." The BARF ion is also abbreviated BArF24−, to distinguish it from the closely related BArF−
20, [(C6F5)4B]−. However, for a small group of chemists, the anion is abbreviated as TFPB otherwise, short for Tetrakis[3,5-bis(triFluoromethyl)Phenyl]Borate.

<span class="mw-page-title-main">Potassium octachlorodirhenate</span> Chemical compound

Potassium octachlorodirhenate(III) is an inorganic compound with the formula K2Re2Cl8. This dark blue salt is well known as an early example of a compound featuring quadruple bond between its metal centers. Although the compound has no practical value, its characterization was significant in opening a new field of research into complexes with quadruple bonds.

<span class="mw-page-title-main">Polytelluride</span>

In chemistry, a polytelluride usually refers to anions of the formula (Ten)2-. Many main group and transition metals form complexes with polytelluride anions.

<span class="mw-page-title-main">Polyselenide</span>

In chemistry, a polyselenide usually refers to anions of the formula (Sen)2-, where Se is the atomic symbol for the element selenium. Many main group and transition metals form complexes with polyselenide anions.

References

  1. ↑ Alberto, R.; Ortner, K.; Wheatley, N.; Schibli, R.; Schubiger, A. P. (2001). "Synthesis and properties of boranocarbonate: a convenient in situ CO source for the aqueous preparation of [99mTc(OH2)3(CO)3]+". J. Am. Chem. Soc. 121 (13): 3135–3136. doi:10.1021/ja003932b. PMID   11457025.
  2. ↑ Von Zelewsky, A. (1995). Stereochemistry of Coordination Compounds . Chichester: John Wiley. ISBN   0-471-95057-2.
  3. ↑ Lehn, J. M. (1995). Supramolecular Chemistry: Concepts and Perspectives. Weinheim: VCH.
  4. ↑ MacGillivray, Leonard R.; Atwood, Jerry L. (1999). "Structural Classification and General Principles for the Design of Spherical Molecular Hosts". Angewandte Chemie International Edition. 38 (8): 1018–1033. doi:10.1002/(SICI)1521-3773(19990419)38:8<1018::AID-ANIE1018>3.0.CO;2-G. PMID   25138490.
  5. ↑ 23978-09-8
  6. ↑ Kim, J.; Ichimura, A. S.; Huang, R. H.; Redko, M.; Phillips, R. C.; Jackson, J. E.; Dye, J. L. (1999). "Crystalline Salts of Na− and K− (Alkalides) that Are Stable at Room Temperature". J. Am. Chem. Soc. 121 (45): 10666–10667. doi:10.1021/ja992667v.
  7. ↑ Valeur, B. (2000). "Design principles of fluorescent molecular sensors for cation recognition". Coordination Chemistry Reviews. 205: 3–40. doi:10.1016/S0010-8545(00)00246-0.
  8. ↑ Beer, Paul D.; Gale, Philip A. (2001). "Anion Recognition and Sensing: The State of the Art and Future Perspectives". Angewandte Chemie International Edition. 40 (3): 486–516. doi:10.1002/1521-3773(20010202)40:3<486::AID-ANIE486>3.0.CO;2-P. PMID   11180358. S2CID   22334242.
  9. ↑ Danil de Namor, Angela; Ghousseini, Lily; Lee, Walter (1985). "Stability constants and free energies of complexation of metal-ion cryptates in nitromethane. Derived parameters for the extraction of cations by cryptand 222 from water to pure nitromethane". Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases. 81 (10): 2495–2502. doi:10.1039/F19858102495.
  10. ↑ Dietrich, B. (1996). "Cryptands". In Gokel, G. W. (ed.). Comprehensive Supramolecular Chemistry. Vol. 1. Oxford: Elsevier. pp. 153–211. ISBN   0-08-040610-6.
  11. ↑ Dye, J. L. (2003). "Electrons as Anions". Science . 301 (5633): 607–608. doi:10.1126/science.1088103. PMID   12893933. S2CID   93768664.
  12. ↑ Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN   0-12-352651-5
  13. ↑ Edwards, Paul A.; Corbett, John D. (1977). "Stable Homopolyatomic Anions. Synthesis and Crystal Structures of Salts Containing the Pentaplumbide(2-) and Pentastannide(2-) Anions". Inorganic Chemistry. 16 (4): 903–907. doi:10.1021/ic50170a036.
  14. ↑ Landini, D.; Maia, A.; Montanari, F.; Tundo, P. (1979). "Lipophilic [2.2.2]cryptands as phase-transfer catalysts. Activation and Nucleophilicity of Anions in Aqueous-Organic Thirteen-Phase Systems and in Organic Solvents of Low Polarity". J. Am. Chem. Soc. 101 (10): 2526–2530. doi:10.1021/ja00504a004.

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