15-Crown-5

Last updated
15-Crown-5
15-crown-5 skeletal.svg
15-Crown-5-3D-balls.png
Names
Preferred IUPAC name
1,4,7,10,13-Pentaoxacyclopentadecane [1]
Identifiers
3D model (JSmol)
1618144
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.046.694 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 251-379-6
3897
MeSH 15-Crown-5
PubChem CID
RTECS number
  • SB0200000
  • InChI=1S/C10H20O5/c1-2-12-5-6-14-9-10-15-8-7-13-4-3-11-1/h1-10H2 Yes check.svgY
    Key: VFTFKUDGYRBSAL-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C10H20O5/c1-2-12-5-6-14-9-10-15-8-7-13-4-3-11-1/h1-10H2
    Key: VFTFKUDGYRBSAL-UHFFFAOYAH
  • C1COCCOCCOCCOCCO1
Properties
C10H20O5
Molar mass 220.265 g·mol−1
AppearanceClear, colorless liquid
Density 1.113 g cm−3 (at 20 °C)
Boiling point 93–96 °C (199–205 °F; 366–369 K) at 0.05 mmHg
log P -0.639
1.465
Thermochemistry
-881.1--877.1 kJ mol−1
-5.9157--5.9129 MJ mol−1
Hazards
GHS labelling:
GHS-pictogram-exclam.svg
Warning
H302, H315, H319
P305+P351+P338
NFPA 704 (fire diamond)
NFPA 704.svgHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
2
1
0
Flash point 113 °C (235 °F; 386 K)
Safety data sheet (SDS) msds.chem.ox.ac.uk
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

15-Crown-5 is a crown ether with the formula (C2H4O)5. It is a cyclic pentamer of ethylene oxide that forms complex with various cations, including sodium (Na+) [2] and potassium (K+); [3] however, it is complementary to Na+ and thus has a higher selectivity for Na+ ions.

Contents

Synthesis

15-Crown-5 can be synthesized using a modified Williamson ether synthesis: [4]

(CH2OCH2CH2Cl)2 + O(CH2CH2OH)2 + 2 NaOH → (CH2CH2O)5 + 2 NaCl + 2 H2O

It also forms from the cyclic oligomerization of ethylene oxide in the presence of gaseous boron trifluoride. [5]

Properties

Analogous to 18-crown-6, 15-crown-5 binds to sodium ions. Thus, when treated with this complexing agent, sodium salts often become soluble in organic solvents.

First-row transition metal dications fit snugly inside the cavity of 15-crown-5. They are too small to be included in 18-crown-6. The binding of transition metal cations results in multiple hydrogen-bonded interactions from both equatorial and axial aqua ligands, such that highly crystalline solid-state supramolecular polymers can be isolated. Metal salts isolated in this form include Co(ClO4)2, Ni(ClO4)2, Cu(ClO4)2, and Zn(ClO4)2. Seven coordinate species are most common for transition metal complexes of 15-crown-5, with the crown ether occupying the equatorial plane, along with 2 axial aqua ligands. [6]

The structure of the complex [Co(15-crown-5)(H2O)2]. Cobalt complex with 15-crown-5.png
The structure of the complex [Co(15-crown-5)(H2O)2].

15-crown-5 has also been used to isolate salts of oxonium ions. For example, from a solution of tetrachloroauric acid, the oxonium ion [H7O3]+ has been isolated as the salt [(H7O3)(15-crown-5)2][AuCl4]. Neutron diffraction studies revealed a sandwich structure, which shows a chain of water with remarkably long O-H bond (1.12 Å) in the acidic proton, but with a very short OH•••O distance (1.32 Å). [6]

Structure of [(H7O3)(15-crown-5)2] ion ((H7O3)(15-crown-5))+.jpg
Structure of [(H7O3)(15-crown-5)2] ion

A derivative of 15-crown-5, benzo-15-crown-5, has been used to produce anionic complexes of carbido ligands as their [K(benzo-15-crown-5)2]+ salts: [6]

(Ar2N)3MoCH + KCH2Ph + 2 (15-crown-5) → [K(15-crown-5)2]+[(Ar2N)3MoC] + CH3Ph

See also

Related Research Articles

In chemistry, an oxonium ion is any cation containing an oxygen atom that has three bonds and 1+ formal charge. The simplest oxonium ion is the hydronium ion.

<span class="mw-page-title-main">Tetraethylammonium</span> Polyatomic ion (N(C₂H₅)₄, charge +1)

Tetraethylammonium (TEA) is a quaternary ammonium cation with the chemical formula [Et4N]+, consisting of four ethyl groups attached to a central nitrogen atom. It is a counterion used in the research laboratory to prepare lipophilic salts of inorganic anions. It is used similarly to tetrabutylammonium, the difference being that its salts are less lipophilic, more easily crystallized and more toxic.

<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.

<span class="mw-page-title-main">Cryptand</span> Cyclic, multidentate ligands adept at encapsulating cations

In chemistry, cryptands are a family of synthetic, bicyclic and polycyclic, multidentate ligands for a variety of cations. 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. 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.

<span class="mw-page-title-main">Pertechnetate</span> Chemical compound or ion

The pertechnetate ion is an oxyanion with the chemical formula TcO
4
. It is often used as a convenient water-soluble source of isotopes of the radioactive element technetium (Tc). In particular it is used to carry the 99mTc isotope which is commonly used in nuclear medicine in several nuclear scanning procedures.

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 is solvent- and temperature-dependent. Below 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.

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.

<span class="mw-page-title-main">Vanadium hexacarbonyl</span> Chemical compound

Vanadium hexacarbonyl is the inorganic compound with the formula V(CO)6. It is a blue-black volatile solid. This highly reactive species is noteworthy from theoretical perspectives as a rare isolable homoleptic metal carbonyl that is paramagnetic. Most species with the formula Mx(CO)y follow the 18-electron rule, whereas V(CO)6 has 17 valence electrons.

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">Chloroauric acid</span> Chemical compound

Chloroauric acid is an inorganic compound with the chemical formula H[AuCl4]. It forms hydrates H[AuCl4nH2O. Both the trihydrate and tetrahydrate are known. Both are orange-yellow solids consisting of the planar [AuCl4] anion. Often chloroauric acid is handled as a solution, such as those obtained by dissolution of gold in aqua regia. These solutions can be converted to other gold complexes or reduced to metallic gold or gold nanoparticles.

<span class="mw-page-title-main">12-Crown-4</span> Chemical compound

12-Crown-4, also called 1,4,7,10-tetraoxacyclododecane and lithium ionophore V, is a crown ether with the formula C8H16O4. It is a cyclic tetramer of ethylene oxide which is specific for the lithium cation.

<span class="mw-page-title-main">Sodium tetraphenylborate</span> Chemical compound

Sodium tetraphenylborate is the organic compound with the formula NaB(C6H5)4. It is a salt, wherein the anion consists of four phenyl rings bonded to boron. This white crystalline solid is used to prepare other tetraphenylborate salts, which are often highly soluble in organic solvents. The compound is used in inorganic and organometallic chemistry as a precipitating agent for potassium, ammonium, rubidium, and caesium ions, and some organic nitrogen compounds.

<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">Brookhart's acid</span> Chemical compound

Brookhart's acid is the salt of the diethyl ether oxonium ion and tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BAr′4). It is a colorless solid, used as a strong acid. The compound was first reported by Volpe, Grant, and Brookhart in 1992.

In coordination chemistry, a macrocyclic ligand is a macrocyclic ring having at least nine atoms and three or more donor sites that serve as ligands. Crown ethers and porphyrins are prominent examples. Macrocyclic ligands often exhibit high affinity for metal ions, the macrocyclic effect.

<span class="mw-page-title-main">Transition metal pyridine complexes</span>

Transition metal pyridine complexes encompass many coordination complexes that contain pyridine as a ligand. Most examples are mixed-ligand complexes. Many variants of pyridine are also known to coordinate to metal ions, such as the methylpyridines, quinolines, and more complex rings.

An arsinide, arsanide, dihydridoarsenate(1−) or arsanyl compound is a chemical derivative of arsine, where one hydrogen atom is replaced with a metal or cation. The arsinide ion has formula AsH−2. It can be considered as a ligand with name arsenido or arsanido. Researchers are unenthusiastic about studying arsanyl compounds, because of the toxic chemicals, and their instability. The IUPAC names are arsanide and dihydridoarsenate(1−). For the ligand the name is arsanido. The neutral −AsH2 group is termed arsanyl.

<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.

<span class="mw-page-title-main">Alkoxide</span> Conjugate base of an alcohol

In chemistry, an alkoxide is the conjugate base of an alcohol and therefore consists of an organic group bonded to a negatively charged oxygen atom. They are written as RO, where R is the organyl substituent. Alkoxides are strong bases and, when R is not bulky, good nucleophiles and good ligands. Alkoxides, although generally not stable in protic solvents such as water, occur widely as intermediates in various reactions, including the Williamson ether synthesis. Transition metal alkoxides are widely used for coatings and as catalysts.

References

  1. "15-crown-5 - Compound Summary". PubChem Compound. USA: National Center for Biotechnology Information. 16 September 2004. Identification and Related Records. Retrieved 11 October 2011.
  2. Takeda, Y.; et al. (1988). "A Conductance Study of 1:1 Complexes of 15-Crown-5, 16-Crown-5, and Benzo-15-crown-5 with Alkali Metal Ions in Nonaqueous Solvents". Bulletin of the Chemical Society of Japan. 61 (3): 627–632. doi: 10.1246/bcsj.61.627 .
  3. Chen, Chun-Yen; et al. (2006). "Potassium ion recognition by 15-crown-5 functionalized CdSe/ZnS quantum dots in H2O". Chem. Comm. (3): 263–265. doi:10.1039/B512677K. PMID   16391728.
  4. Cook, Fred L.; Caruso, Thomas C.; Byrne, Michael P.; Bowers, Chauncey W.; Speck, Don H.; Liotta, Charles L. (1974). "Facile syntheses of 12-crown-4 and 15-crown-5". Tetrahedron Letters. 15 (46): 4029–4032. doi:10.1016/S0040-4039(01)92075-1.
  5. Liotta, Charles L.; Berkner, Joachim (2001), "15-Crown-5", Encyclopedia of Reagents for Organic Synthesis, Chichester, UK: John Wiley & Sons, Ltd, doi:10.1002/047084289x.rc263, ISBN   978-0-471-93623-7
  6. 1 2 3 Jonathan W. Steed; Jerry L. Atwood (2009). Supramolecular Chemistry, 2nd edition. Wiley. ISBN   978-0-470-51233-3.

Further reading