Copper(II) glycinate

Last updated

Contents

Copper(II) glycinate
Cu(gly)2(OH2).png
Structure of the cis monohydrate form of bis(glycinato)copper(II)
Names
IUPAC name
bis(glycinato)copper(II)
Other names
cupric glycinate
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.033.425 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 236-783-2
PubChem CID
UNII
  • InChI=1S/2C2H5NO2.Cu/c2*3-1-2(4)5;/h2*1,3H2,(H,4,5);/q;;+2/p-2
    Key: VVYPIVJZLVJPGU-UHFFFAOYSA-L
  • C(C(=O)[O-])N.C(C(=O)[O-])N.[Cu+2]
Properties
C4H10CuN2O5
Molar mass 229.679 g·mol−1
Appearancelight blue, flake-like crystals (cis form)
Density 2.029 g/cm3
Melting point 212 °C (414 °F; 485 K) (decomp.)
0.18 g/100 g (0 °C)
0.52 g/100 g (25 °C)
Solubility soluble in DMF, DMSO, pyridine; slightly soluble in ethanol
Structure [1]
Orthorhombic
№ 19 (P212121)
222
a = 5.21 Å, b = 10.81 Å, c = 13.49 Å
4
Hazards
GHS labelling:
GHS-pictogram-exclam.svg GHS-pictogram-pollu.svg
Warning
H302, H315, H319, H400
P264, P270, P273, P280, P301+P312, P302+P352, P305+P351+P338, P321, P330, P332+P313, P337+P313, P362, P391, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Copper(II) glycinate (IUPAC suggested name: bis(glycinato)copper(II)) refers to the coordination complex of copper(II) with two equivalents of glycinate, with the formula [Cu(glycinate)2(H2O)x] where x = 1 (monohydrate) or 0 (anhydrous form). The complex was first reported in 1841, and its chemistry has been revisited many times, particularly in relation to the isomerisation reaction between the cis and trans forms which was first reported in 1890. [2] [3]

All forms are blue solids, with varying degrees of water solubility. A practical application of the compound is as a source of dietary copper in animal feeds. [4]

Synthesis

Bis(glycinato)copper(II) is typically prepared from the reaction of copper(II) acetate in aqueous ethanol with glycine: [2] [3]

Cu(OAc)2 + 2 H2NCH2COOH + x H2O → [Cu(H2NCH2COO)2(H2O)x] + 2 AcOH, x = 0 or 1

The reaction proceeds through a non-redox dissociative substitution mechanism and usually affords the cis isomer. [2] [3]

Structure

Like most amino acid complexes, the glycinate forms a 5-membered chelate ring, with the glycinato ligand serving as a bidentate (κ2Ο,Ν) species. [2] [5] The chelating ligands assume a square planar configuration around the copper atom as is common for tetracoordinate d9 complexes, calculated to be much lower in energy than the alternative tetrahedral arrangement. [3]

Cis and trans isomerism

The unsymmetric nature of the ligand and square planar coordination thereof gives rise to two possible geometric isomers: a cis and a trans form.

Multiple ways of differentiating the geometric isomers exist, an easily accessible one being IR spectroscopy with the characteristic number of C–N, C–O, and CuII–N identifying the ligand configuration. Crystal appearance may also be of some value for isomer indication, though the ultimate diagnostic technique is X-ray crystallography. [1]

All forms of the complex have been characterized crystallographically, the most commonly isolated one being the cis monohydrate (x = 1). [5] [1]

Isomerisation of the cis to the trans form occurs at high temperatures via a ring-twisting mechanism. [2] [3]

Related Research Articles

<span class="mw-page-title-main">Coordination complex</span> Molecule or ion containing ligands datively bonded to a central metallic atom

A coordination complex is a chemical compound consisting of a central atom or ion, which is usually metallic and is called the coordination centre, and a surrounding array of bound molecules or ions, that are in turn known as ligands or complexing agents. Many metal-containing compounds, especially those that include transition metals, are coordination complexes.

<span class="mw-page-title-main">Peptide bond</span> Covalent chemical bond between amino acids in a peptide or protein chain

In organic chemistry, a peptide bond is an amide type of covalent chemical bond linking two consecutive alpha-amino acids from C1 of one alpha-amino acid and N2 of another, along a peptide or protein chain.

<span class="mw-page-title-main">Copper(II) nitrate</span> Chemical compound

Copper(II) nitrate describes any member of the family of inorganic compounds with the formula Cu(NO3)2(H2O)x. The hydrates are hygroscopic blue solids. Anhydrous copper nitrate forms blue-green crystals and sublimes in a vacuum at 150-200 °C. Common hydrates are the hemipentahydrate and trihydrate.

<span class="mw-page-title-main">Metal ammine complex</span> Class of chemical compounds

In coordination chemistry, metal ammine complexes are metal complexes containing at least one ammonia ligand. "Ammine" is spelled this way for historical reasons; in contrast, alkyl or aryl bearing ligands are spelt with a single "m". Almost all metal ions bind ammonia as a ligand, but the most prevalent examples of ammine complexes are for Cr(III), Co(III), Ni(II), Cu(II) as well as several platinum group metals.

1,5-Cyclooctadiene is a cyclic hydrocarbon with the chemical formula C8H12, specifically [−(CH2)2−CH=CH−]2.

<span class="mw-page-title-main">Nickel(II) bis(acetylacetonate)</span> Coordination complex

Nickel(II) bis(acetylacetonate) is a coordination complex with the formula [Ni(acac)2]3, where acac is the anion C5H7O−2 derived from deprotonation of acetylacetone. It is a dark green paramagnetic solid that is soluble in organic solvents such as toluene. It reacts with water to give the blue-green diaquo complex Ni(acac)2(H2O)2.

<span class="mw-page-title-main">Dichlorotris(triphenylphosphine)ruthenium(II)</span> Chemical compound

Dichlorotris(triphenylphosphine)ruthenium(II) is a coordination complex of ruthenium. It is a chocolate brown solid that is soluble in organic solvents such as benzene. The compound is used as a precursor to other complexes including those used in homogeneous catalysis.

Metal acetylacetonates are coordination complexes derived from the acetylacetonate anion (CH
3
COCHCOCH
3
) and metal ions, usually transition metals. The bidentate ligand acetylacetonate is often abbreviated acac. Typically both oxygen atoms bind to the metal to form a six-membered chelate ring. The simplest complexes have the formula M(acac)3 and M(acac)2. Mixed-ligand complexes, e.g. VO(acac)2, are also numerous. Variations of acetylacetonate have also been developed with myriad substituents in place of methyl (RCOCHCOR). Many such complexes are soluble in organic solvents, in contrast to the related metal halides. Because of these properties, acac complexes are sometimes used as catalyst precursors and reagents. Applications include their use as NMR "shift reagents" and as catalysts for organic synthesis, and precursors to industrial hydroformylation catalysts. C
5
H
7
O
2
in some cases also binds to metals through the central carbon atom; this bonding mode is more common for the third-row transition metals such as platinum(II) and iridium(III).

<span class="mw-page-title-main">Metal-phosphine complex</span>

A metal-phosphine complex is a coordination complex containing one or more phosphine ligands. Almost always, the phosphine is an organophosphine of the type R3P (R = alkyl, aryl). Metal phosphine complexes are useful in homogeneous catalysis. Prominent examples of metal phosphine complexes include Wilkinson's catalyst (Rh(PPh3)3Cl), Grubbs' catalyst, and tetrakis(triphenylphosphine)palladium(0).

Nickel(II) nitrite is an inorganic compound with the chemical formula Ni(NO2)2. Anhydrous nickel nitrite was first discovered in 1961 by Cyril Clifford Addison, who allowed gaseous nickel tetracarbonyl to react with dinitrogen tetroxide, yielding a green smoke. Nickel nitrite was the second transition element anhydrous nitrite discovered after silver nitrite.

<span class="mw-page-title-main">Dichlorobis(triphenylphosphine)nickel(II)</span> Chemical compound

Dichlorobis(triphenylphosphine)nickel(II) refers to a pair of metal phosphine complexes with the formula NiCl2[P(C6H5)3]2. The compound exists as two isomers, a paramagnetic dark blue solid and a diamagnetic red solid. These complexes function as catalysts for organic synthesis.

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

trans-Dichlorodiammineplatinum(II) is the trans isomer of the coordination complex with the formula trans-PtCl2(NH3)2, sometimes called transplatin. It is a yellow solid with low solubility in water but good solubility in DMF. The existence of two isomers of PtCl2(NH3)2 led Alfred Werner to propose square planar molecular geometry. It belongs to the molecular symmetry point group D2h.

<span class="mw-page-title-main">Salpn ligand</span> Chemical compound

Salpn is the common name for a chelating ligand, properly called N,N-bis(salicylidene)-1,2-propanediamine, used as a motor oil additive.

Transition metal amino acid complexes are a large family of coordination complexes containing the conjugate bases of the amino acids, the 2-aminocarboxylates. Amino acids are prevalent in nature, and all of them function as ligands toward the transition metals. Not included in this article are complexes of the amides and ester derivatives of amino acids. Also excluded are the polyamino acids including the chelating agents EDTA and NTA.

<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.

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

Transition metal dithiocarbamate complexes are coordination complexes containing one or more dithiocarbamate ligand, which are typically abbreviated R2dtc. Many complexes are known. Several homoleptic derivatives have the formula M(R2dtc)n where n = 2 and 3.

<span class="mw-page-title-main">Transition metal nitrite complex</span> Chemical complexes containing one or more –NO₂ ligands

In organometallic chemistry, transition metal complexes of nitrite describes families of coordination complexes containing one or more nitrite ligands. Although the synthetic derivatives are only of scholarly interest, metal-nitrite complexes occur in several enzymes that participate in the nitrogen cycle.

<span class="mw-page-title-main">Copper(II) oxalate</span> Chemical compound

Copper(II) oxalate are inorganic compounds with the chemical formula CuC2O4(H2O)x. The value of x can be 0, 0.44, and 1. Two of these species are found as secondary minerals, whewellite (monohydrate) and moolooite. The anhydrous compound has been characterized by X-ray crystallography. Many transition metal oxalate complexes are known.

cis-1,2-Bis(diphenylphosphino)ethylene (dppv) is an organophosphorus compound with the formula C2H2(PPh2)2 (Ph = C6H5). Both the cis and trans isomers are known, but the cis isomer is of primary interest. Classified as a diphosphine ligand, it is a bidentate ligand in coordination chemistry. For example it gives rise to the complex Ni(dppv)2 and the coordination polymer [Ni(dppv)]n. As a chelating ligand, dppv is very similar to 1,2-bis(diphenylphosphino)benzene.

Transition metal complexes of thiocyanate describes coordination complexes containing one or more thiocyanate (SCN-) ligands. The topic also includes transition metal complexes of isothiocyanate. These complexes have few applications but played significant role in the development of coordination chemistry.

References

  1. 1 2 3 Köse DA, Toprak E, Kaşarcı A, Avcı E, Avcı GA, Şahin O, et al. (2 July 2016). "Synthesis, Spectral, and Thermal Studies of Co(II), Ni(II), Cu(II), and Zn(II)-Glycinato Complexes and Investigation of Their Biological Properties: Crystal Structure of [Cu(µ-gly) 2 (H 2 O)] n". Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry. 46 (7): 1109–1118. doi:10.1080/15533174.2013.801855. ISSN   1553-3174. S2CID   101548954.
  2. 1 2 3 4 5 Delf BW, Gillard RD, O'Brien P (1 January 1979). "The isomers of α-amino-acids with copper(II). Part 5. The cis and trans isomers of bis(glycinato)copper(II), and their novel thermal isomerization". Journal of the Chemical Society, Dalton Transactions (8): 1301–1305. doi:10.1039/DT9790001301. ISSN   1364-5447.
  3. 1 2 3 4 5 Tautermann CS, Sabolović J, Voegele AF, Liedl KR (1 February 2004). "Mechanism of the Cis−Trans Isomerization of Bis(glycinato)copper(II)". The Journal of Physical Chemistry B. 108 (6): 2098–2102. doi:10.1021/jp0364497. ISSN   1520-6106.
  4. Ward JD, Spears JW (1997). "Long-Term Effects of Consumption of Low-Copper Diets with or Without Supplemental Molybdenum on Copper Status, Performance, and Carcass Characteristics of Cattle". Journal of Animal Science. 75 (11): 3057–3065. doi: 10.2527/1997.75113057x . PMID   9374323.
  5. 1 2 Casari BM, Mahmoudkhani AH, Langer V (2004). "A Redetermination of cis-Aquabis(glycinato-κ2N,O)copper(II)". Acta Crystallogr. E. 60 (12): m1949–m1951. doi:10.1107/S1600536804030041.