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World Applied Programming, Vol ( 2 ), Issue ( 10 ), October 2012. 4 31 - 443 ISSN: 2222- 2510 ©2012 WAP journal. www.waprogramming.com
Coordination Chemistry of
Copper α- Amino Acid Complexes
Mohammad Hakimi Tahereh Saberi Aliabadi
Chemistry Department Chemistry Department Payame Noor University Payame Noor University 19395 - 4697 Tehran 19395 - 4697 Tehran [email protected] Abstract: This review gives an overview on structures and Coordination chemistry of copper amino acid complexes. A comprehensive review, >120 references, on copper complexes of the amino acids is presented. Key word: copper, copper complexes, α- amino acid, Coordination chemistry I. INTRODUCTION Copper like all metals forms coordination complexes with ligands too. Copper (II) forms stable complexes with amino acids through chelating. Sometimes Copper and amino acids form oxo complexes, which also feature copper(III) [1]. With di- and tripeptides, purple-colored copper(III) complexes are stabilized by the deprotonated amide ligands [2]. Amino acids having both the amine and carboxylic acid groups attached to the first, or alpha, carbon atom have particular importance in biochemistry. They are known as 2 - , alpha-, or α-amino acids (generic formula H 2 NCHRCOOH in most cases[3][4 ] where R is an organic substituent known as a "side-chain")[5]; 9 of the 20 standard amino acids are called "essential" amino acids for humans because they cannot be created from other compounds by the human body, and so must be taken in as food. Others may be conditionally essential for some ages or medical conditions. Essential amino acids may also differ between species [6-8]. Copper α amino acid complex attracts attention of chemists because of its different kind of applications. In copper α amino acid complexes syntheses, the amino acid is first reacted with a copper (II) ion and gives a stable square planar copper (II) complex. Subsequently, the copper–amino acid complex is reacted with the amino acid side-chain protecting reagent as the a-amino and a-carboxyl groups are bound to copper (II); the protecting group selectively reacts with the side-chain functional group of a given amino acid. In our previous investigations structures and Coordination chemistry of some copper complexes were reported [9, 10]. In this review an overview on structures and Coordination chemistry of copper amino acid complexes is given. A comprehensive review, >120 references, on copper complexes of the amino acids is presented. II. COORDINATION CHEMISTRY OF Α-AMINO ACID COMPLEXES II.1. GLYCINE A new compound [(Gly) 2 Cu][Na(H 2 O) 4 Cr(OH) 6 Mo 6 O 18 ] · 9.5H 2 O (Gly=glycine), has been synthesized. The Compound exhibits an unusual two-dimensional (2D) window-like network constructed from [Cr(OH) 6 Mo 6 O 18 ]^3 −^ as building blocks, Na+^ ions and Cu2+^ coordination complexes as linkers [11]. A novel compound contains hexanuclear copper cluster and octamolybdate cluster {[NaCu 6 (Gly) 8 (H 2 O) 2 ][Mo 8 O 26 (GlyH) 2 (Cu(Gly)H 2 O)] 2 }{NaCu 6 (Gly) 8 (H 2 O) 2 }{Mo 8 O 26 (GlyH) 2 }·16H 2 O has been synthesized. The magnetic measurement of shows that ferromagnetic coupling exists between the magnetic centers of the hexanuclear copper cluster [12]. The decavanadate with a novel glycine–glycinato complex of copper (II) in the cationic part, (NH 4 ) 2 [Cu 2 (H 2 O) 4 (NH 3 CH 2 COO) 2 (NH 2 CH 2 COO) 2 ]H 2 V 10 O 28 ·6H 2 O, has been prepared. An X-ray structure analysis revealed that the structure contains cationic copper complex with a rare Cu (H 2 O) 2 Cu double bridge. In this cation, a simultaneous bidentate N, O– and monodentate O– coordination of glycine to the same central atom was observed for the first time [13]. The compound, [Cu (C 2 H 4 NO 2 )Cl(C 10 H 8 N 2 )]·2H 2 O reported [14]. And the compound, [Cu(C 2 H 4 NO 2 ) 2 (H 2 O)], reported by Freeman et al [15]. The compound, trans-[Cu (gly) 2 ]·4-BrC 6 H 4 OH, when trans-bis(glycinato-N,O)copper(II) and 4-bromophenol were allowed to stand in water for several days are
synthesized. Structural analysis reveals that the 4-bromophenol is not coordinated to the copper and that the glycinato units are trans in N, O-bidentate binding mode. The molecule shows Cu atom in a [4 + 2] coordination mode [16]. A copper(II) coordination polymer with ligation from adenine, glycine, one nitrate anion and a water molecule giving a distorted octahedral coordination geometry with N 3 O 3 donor set. Each chain is hydrogen-bonded through C–H⋯O and N–H⋯O interactions on both sides leading to an overall polymeric structure [17]. The crystal structure of bisglycino-copper (II) monohydrate was determined. Two glycine molecules are coordinated to the copper (II) ion, forming a planar cis configuration. The irregular octahedral coordination is completed by two oxygen atoms:one belonging to a water molecule and the other a free carboxyl oxygen atom of an adjacent asymmetric unit [18]. Structures of chloro(glycinato)(1,10-phenanthroline)copper(II) monohydrate has been synthesizd. The Cu ion displays distorted square-pyramidal coordination with the chlorine atom or the water molecule in the apical position [19]. Structures of aqua(4,7-dimethyl-1,10-phenanthroline)(glycinato)(nitrato)copper(II) monohydrate has been synthesizd. The Cu ion displays distorted octahedral coordination [20]. syntheses and structures of chloro(glycinato)(methanol)copper(II) and chloro(glycinato)(1-methylimidazole)copper(II) are reported [21].The compound [Cu(C 2 H 4 NO 2 )(C 16 H 16 N 2 )(H 2 O)NO 3 ] has been synthesizd. The Cu ion displays distorted square-pyramidal coordination Where the water molecule is in the apical position and the base is defined by the N and one of the O atoms from the glycine ligand, and both phenanthroline N atoms [22]. Coordination polymer and Cu 3 (Gly) 4 (H 2 O) 2 (NO 3 ) 2 was synthesized and characterized structurally.The compound is polymeric chain, consisting from trinuclear blocks Cu 3 (Gly) 4 (H 2 O) 2 2+. Cu(II) ions are linked by carboxyl-group, while trinuclear units Cu 3 (Gly) 4 (H 2 O) 2 2+^ are linked by NO 3 −^ ions, acting as the bridges between Cu(II) ions of neighboring trinuclear units [23]. The syntheses, structures, and characterization of six Ln3+–Cu2+–glycine (Hgly) coordination polymers are described [24]. A novel bis(glycinato)copper(II)paradodecatungstate Na 8 [{Cu(gly) 2 } 2 ]-{H 2 (H 2 W 12 O 42 )}] · 24H 2 O has been synthesized under hydrothermal conditions [25]. A novel 3D compound, {K 3 H 2 [Cu(Gly) 2 ] 3 BW 12 O 40 }·10H 2 O (Gly = glycine), has been synthesized. The Compound contains square-grid layers constructed by potassium cations and copper-glycine coordination complexes, the [BW 12 O 40 ]^4 −^ anions as templates are accommodated in the square grids by connecting with the K atoms. The K atoms link [BW 12 O 40 ]^4 −^ anions from different layers together to yield a 3D novel structure [26]. The copper(II)-glycine-thiocyanate ion system has been studied. The IR spectrum of the solid complex suggests an aquo ligand, a bridging thiocyanato ligand and a N,O-bidentate chelating glycinato ligand. for the complex [Cu(glycinato)(NCS)(H 2 O)]n a tetragonally distorted octahedral structure suggested [27]. Compound Coordination number Ref. catena-(hexakis(m3-Hydroxo)-decakis(m2-oxo)-tetraaqua-diglycineoctaoxo-chromium-copper-hexa- molybdenum-sodium hydrate clathrate)
6 [11]
octakis(m3-Glycinato-N,O,O')-diaqua-hexa-copper(ii)-sodium(i) bis(m4-oxo)-tetrakis(m3-oxo)- hexakis(m2-oxo)-bis(glycine-O)-tetradeca-oxoocta-molybdenum(vi) tetrakis(m4-oxo)-octakis(m3- glycinato-N,O,O')-octakis(m3-oxo)-bis(m2-glycine-O,O')-hexadecakis(m2-oxo)-tetra- aquabis(glycine-N,O)-bis(glycine-O)-tetracosa-oxo-octa-copper(ii)-hexadecamolybdenum(vi)- sodium(i) heptadecahydrate
5 [12]
diammonium bis(m2-aqua)-tetraaqua-bis(glycinato)-bis(glycine)-dicopper(ii) bis(m6-oxo)-bis(m3- hydroxo)-bis(m3-oxo)-tetradecakis(m2-oxo)-octaoxo-tetra-vanadium hexahydrate
6 [13]
(2,2'-Bipyridyl-k2N,N')-chloro-(glycinato-k2N,O)-copper(ii) dihydrate 5 [14] cis-Aqua-bis(glycinato-N,O)-copper(ii) 5 [15] catena-(trans-bis(Glycinato-N,O)-copper(ii)4- bromophenol solvate) 5 [16] catena-[(m2-Adenine)-aqua-(glycinato-N,O)-nitrato-copper(ii)] 6 [17] cis-bis(Glycinato-N,O)-copper(ii) monohydrate 4 [18] Chloro-(glycinato-N,O)-(1,10-phenanthroline-N,N')-copper(ii) monohydrate 5 [19] Aqua-glycinato-(4,7-dimethyl-1,10-phenanthrolinato)-nitrato-copper(ii) monohydrate 6 [20] catena-(m2-Chloro-(glycinato-N,O,O')-(1-methylimidazole-N)-copper(ii)) 5 [21] Aqua-(glycinato-N,O)-(3,4,7,8-tetramethyl-1,10-phenanthrolinato-N,N')- copper(ii) nitrate 5 [22] catena-(bis(m2-Glycinato)-bis(m2-nitrato-O,O')-diaqua-bis(glycinato-N,O) - tri-copper(ii)) [23] catena-(Di-sodium (m10-perchlorato)-decakis(m3-glycinato)-octacosakis(m3-hydroxo)-tetrakis(m2- 2 - ammonioacetato)-bis(m2-glycinato)-hexakis(m2-glycinato)-tetradeca-aqua-hexa-europiumpentacosa- copper tricosaperchlorate hydrate)
[24]
catena-(Octa-sodium bis(m3-hydroxo)-tetrakis(m3-oxo)-bis(m2-hydroxo)-icosakis(m2-oxo)- tetradecaoxo-tetrakis(glycine-N,O)-di-copper(ii)-dodeca-tungsten hydrate)
6 [25]
catena-((m12-tetraoxoborato)-bis(m3-glycinato)-bis(m3-oxo)-tris(m2-glycinato)-bis(m2-hydroxo)- (m2-aqua)-pentacontakis(m2-oxo)-pentaaqua-(glycinato)-heptaoxo-tri-copper-tri-potassium- dodecatungstentetrahydrate)
4 [26]
complexes [Cu(DL-alaO) 2 (H 2 O)], [Cu(L-alaO) 2 ] [alaO = alaninate(1–)] are reported. The single-crystal e.s.r. spectrum of cis - [Cu(glyO) 2 (H 2 O)][glyO = glycinate(1–)] was also measured, and the small in-plane anisotropy of the molecular g tensor confirmed the interpretation of the g values of the trans amino acid complexes. Angular overlap calculations of the d – d transition energies and molecular g values of the complexes suggest metal–ligand bonding parameters consistent with their molecular structures. However, in agreement with similar findings on analogous compounds the dz^2 → dx^2 – y^2 transitions were found to lie at anomalously high energy, this discrepancy being most marked when the axial bonds are very long [66]. three sodium-centered polynuclear octahedral copper(II)–amino acid clusters, [Na⊂{Cu 6 (Ala) 8 (H 2 O)(ClO 4 )}] · 4ClO 4 · 4H 2 O ( a ), Na[Na⊂{Cu 6 (Ala) 8 (ClO 4 )}] 2 · 9ClO 4 · 8H 2 O ( b ), and [Na⊂{Cu 5 (Ala) 6 (H 2 O) 3 }] n · 5 n (ClO 4 ) · 3 n (H 2 O) ( c ) (Ala = L-alanine), were synthesized. The structures were characterized by X-ray structure analysis. The structure of a can be described as an octahedron formed with six copper atoms in which four Cu(Ala) 2 ligands bridge two axial copper ions and capture one Na+^ in the center of the cage and that of b as an octahedral dimer that is linked by two carboxylate oxygen atoms. Complex c is a chain composed of incomplete octahedron [NaCu 5 ] units linked together by two carboxylate oxygen atoms. The magnetic susceptibility measurements indicate that all three clusters are ferromagnetic [67]. The crystal and molecular structure of a new crystalline modification of bis-[D-alaninato] copper (II), Cu (C 3 H 6 NO 2 ) 2 ′ has been determined. The inner co-ordination sphere around the copper atom is square pyramidal; the two bidentate α-amino acid rings are cis and form the basal plane of the pyramid, the apex being occupied by a carboxylate oxygen atom, from a neighbouring molecule, at a distance of 2·390(7)Å [68]. Compound Coordination number Ref. trans-bis(DL-a-Alaninato-N,O)-copper(ii) monohydrate 4 [57] trans-bis(L-a-Alaninato)-copper(ii) 4 [58] L-Alaninato-aqua-(4,7-diphenyl-1,1 0 - phenanthrolinato)-copper(ii) nitrite monohydrate 5 [59] bis(D,L-Alaninato-O,N)-copper(ii) monohydrate 4 [60] catena-(bis((m2-4,4'-bipyridyl)-(L-alaninato)-aqua-copper(ii) nitrate) trihydrate) 5 [61] (L-Alaninato)-(aqua)-(1,10-phenanthroline)-copper nitrate hydrate and(Alaninato)-(aqua)-(1,10- phenanthroline-5,6-dione)-copper nitrate
5 [62]
catena-(cis-(m2-L-Alaninato)-(L-alaninato)-copper(ii)) 5 [63] catena-((m2-Alaninato)-aqua-(imidazole)-copper(ii) perchlorate) and catena-((m2-Alaninato)-(m2-perchlorato)-(pyrazole)-copper(ii)) and catena-((m2-Phenylalaninato)- aqua-(imidazole)-copper(ii) perchlorate)
[64]
catena-[(m2-Thiocyanato-N,S)-(D,L-alaninato-N,O)-aqua-copper(ii)] 5 [65] trans-bis(L-Alaninato-N,O)-copper(ii) 4 [66] octakis(m3-Alaninato)-aqua-(perchlorato-O)-hexa-copper(ii)-sodium tetraperchlorate trihydrate 5 [67] catena-(cis-bis(D-Alaninato)-copper(ii)) 5 [68] catena(L-Alaninato-aqua-L-histidinato-copper(ii)) trihydrate 5 [69] Aqua-(L-proline-L-alanine)-copper(ii) sesquihydrate 4 [70] trans-bis(L-Alaninato-N,O)-copper(ii) 4 [71] trans-bis(D,L-Alaninato-N,O)-copper(ii) monohydrate 4 [72] catena-((m2-Aqua)-bis(DL-alaninato-N,O)-copper(ii)) 6 [73] (m2-Dipicolinamideazino)-bis(alanyl)-diaqua-di-copper(ii) dinitrate trihydrate 5 [74] catena-(bis(m2-4,4'-bipyrine-N,N')-(D-alaninato)-(L-alaninato)-diaqua-dicopper(ii) bis(nitrate) trihydrate
5 [75]
catena-((m2-L-Alaninato)-(2,2'-bipyridyl)-copper(ii) perchlorate monohydrate) 5 [76] bis(m4-Alaninato)-tetradecakis(m3-alaninato)-(m2-perchlorato-O,O')-tetra-aqua-bis(perchlorato-O)- dodeca-copper(ii)-tri-sodiumoctaperchlorate tetrahydrate
[77]
catena-(bis(m4-Alaninato-N,O,O,O',O')-tetrakis(m3-alaninato-N,O,O,O')-triaqua-penta-copper(ii)- sodium pentaperchlorate trihydrate)
[78]
catena-((m2-L-Alaninato)-(1,10-phenanthroline)-copper(ii) perchlorate monohydrate) 5 [79]
II.3. ARGININE
Copper(II) complexes [Cu(L-arg) 2 ](NO 3 ) 2 ( 1 ) and [Cu(L-arg)(B)Cl]Cl ( 2 − 5 ), where B is a heterocyclic base, namely, 2,2′-bipyridine (bpy, 2 ), 1,10-phenanthroline (phen, 3 ), dipyrido[3,2-d:2′,3′-f]quinoxaline (dpq, 4 ), and dipyrido[3,2- a:2′,3′-c]phenazine (dppz, 5 ), are prepared. Ternary complex 3 , structurally characterized using X-ray crystallography, shows a square-pyramidal (4 + 1) coordination geometry in which the N,O-donor L-arginine and N,N-donor 1,10- phenanthroline form the basal plane with one chloride at the elongated axial site. The one-electron paramagnetic complexes display a metal-centered d−d band in the range of 590−690 nm in aqueous DMF [80]. Ternary copper(II) complexes containing an acidic amino acid (A) and a basic amino acid (B),Cu(A)(B), where A refers to ethylenediamine-N-monoaceticacid(EDMA) and DL-diaminopropionic acid (DAP) and B to L-arginine and L-lysine, have been investigated. The Cu ion is in a slightly distorted square-pyramidal geometry With the two nitrogen atoms of EDMA and the nitrogen and oxygen atoms of L-Arg coordinated at the equatorial positions and the carboxylate oxygen atom of EDMA coordinated at an axial position. A perchlorate oxygen atom weakly coordinates at the other axial site [81]. The crystal structures of [Cu (L-Arg) 2 ]2+X^2 −^ systems, where X refers to dinegative tetrahedral anions, sulfate or 1,3-benzenedisulfonate ( m - bs^2 −) studied. The molecular structure of [Cu(L- Arg) 2 ](SO 4 ) exhibited a planar Cu(II) geometry with the two coordinated amino groups in the cis configuration due to the hydrogen bonds with SO 4 2 −, and the complex with X^2 −= m - bs^2 −^ assumed the trans configuration without hydrogen bonds with m - bs^2 [82]. The crystal structure of bis(L-arginine)Cu(II)(acetate) 2 trihydrate has been determined by X-ray analysis. Each copper atom has an essentially square planar coordination with the two arginine molecules chelated via the carboxy oxygens and the α-amino nitrogens, but with distorted six-fold coordinations completed by weak Cu…O (acetate) interactions. Electrostatic interactions between the acetates and the protonated ends of the amino acid residues link the two independent [Cu (L-arginine) 2 (acetate) 2 ] units into dimers, which are then connected via hydrogen bonds, also involving the water molecules, into an infinite network [83]. The [Cu(L-Arg) 2 ]2+^ complex ions (Arg=arginine) in the presence of aromatic carboxylates has been studied by spectroscopic and X-ray diffraction methods. [Cu (L-Arg) 2 ]Cl 2 dissolved in aqueous solutions containing benzene-1,4-dicarboxylate (terephthalate, p - pa^2 −) and - 1,2,4,5-tetracarboxylate (pyromellitate, pma^4 −) gave crystals of [Cu(L-Arg) 2 ]( p - pa) · 2H 2 O and [Cu(L- Arg) 2 ] 2 (pma) · 4H 2 O respectively. Both complexes have a square-planar structure with two L-Arg molecules in the trans configuration [84]. The synthesis, characterization and crystal structure of a novel dinuclear copper compound with L-arginine, mono and bidentate HPO 42 −^ oxoanions and an OH−^ anion [Cu 2 (L-arg) 2 (μ-HPO 4 - O)(μ-HPO 4 - O,O′)(μ- OH)]−^ · (H 3 O)+^ · 6H 2 O are reported. The two independent copper ions are in a distorted square pyramidal coordination, each bonded to one L-arginine molecule [85]. Complexes of the type Cu (Arg) 2 · n H 2 0 (L = aromatic dicarboxylate, n = 5,6) formed by self-assembly show double-helical structures in the solid state, which comprise infinite [Cu(Arg) 2 ]2+-L^2 −^ strands [86]. Compound Coordination number Ref. (L-Arginine-N,O)-chloro-(1,10-phenanthroline)-copper(ii) chloride hydrate 5 [80] (L-Arginine)-(ethylenediamine-N-monoacetic acid)-copper(ii) perchlorate ethanol solvate and bis(L-Arginine)-copper(ii) dinitrate trihydrate
[81]
Aqua-bis(L-arginine-N,O)-copper(ii) m-phthalate pentahydrate and Aqua-bis(L-arginine-N,O)- copper(ii) 2,6-dipicolinate tetrahydrate and Aqua-bis(D-arginine-N,O)-copper(ii) 3,5-dipicolinate tetrahydrate
5 [82]
(Acetic acid-O)-bis(L-arginine-N,O)-copper(ii) acetic acid trihydrate 5 [83] bis(L-Arginine-N,O)-copper(ii) terephthalate dihydrate 4 [84] Oxonium (m2-hydrogen phosphato-O,O')-(m2-hydrogen phosphato-O,O)-(m2-hydroxo)-bis(L- arginine-N,O)-di-copper(ii) hexahydrate
5 [85]
Aqua-bis(L-arginine-O,N)-copper(ii) (m-phthalate) pentahydrate 5 [86] catena-[bis(m2-Perchlorato)-bis(L-arginine)-bis(2,2'-bipyridyl)-dicopper(ii) diperchlorate tetrahydrate
6 [87]
trans-bis(L-Arginine-N,O)-(nitrato-O)-copper(ii) nitrate trihydrate 5 [88] catena-(cis-(m2-L-Arginine-N,O,O')-(L-arginine-N,O)-copper(ii) dinitratetrihydrate) 5 [89] Aqua-bis(D-arginine-N,O)-copper(ii) m-phthalate pentahydrate and Aqua-bis(L-arginine-N,O)- copper(ii) sulfate pentahydrate and bis(L-Arginine-N,O)-copper(ii) 1,3-benzenedisulfonate
[90]
Aqua-bis(L-arginine-O,N)-copper(ii) (2,6-dipicolinate) tetrahydrate and Aqua-bis(D-arginine-O,N)- copper(ii) (3,5-dipicolinate) tetrahydrate
5 [91]
Compound Coordination number Ref. bis(L-Histidine) copper(ii) nitrate dihydrate 6 [101] (L-Histidine-N,O)-(1,4,7-triazacyclononane)-copper(ii)bis(hexafluorophosphate) monohydrate 5 [102] Dichloro-(L-histidine)-copper(ii) 4 [103] Dichloro-(3-(1H-imidazol- 3 - ium- 5 - yl)alaninato)-copper hemihydrate 4 [104] (L-Histidine-N,O)-(1,10-phenanthroline)-copper(ii) diperchloratemonohydrate 4 [105] II. 6. LYSINE The crystal and molecular structure of dichloro (d-lysinato (l-lysinato) copper (II) dehydrate has been investigated. The compound was prepared by reacting DL-lysine hydrochloride with basis copper carbonate. Single crystal, suitable for x-ray work, were obtained by slow evaporation of the resulting blue solution over a period of days. The coordination of the copper atom corresponds to a distorted octahedron with four short and two long bonds [106]. The crystal structure of bis(L-lysine)Cu(II) chloride dihydrate has been determined by X-ray analysis. The copper (II) atom has an essentially square planar coordination with the two lysine molecules chelated via the carboxy oxygen and the α- amino nitrogen [107]. Compound Coordination number Ref. (d-Lysinato)-(l-lysinato)-copper(ii) dichloride dihydrate 4 [106] Chloro-bis(L-lysinato-N,O)-copper(ii) chloride dihydrate 5 [107] Chloro-bis(L-lysinato-N,O)-copper(ii) chloride dihydrate 5 [108] II. 7. LEUCINE The crystal structures ternary complexes [Cu(L-Leu)( o - phen)(H 2 O)]NO 3 (1) and [Cu(DL-Leu)( o - phen) (H 2 O)]NO 3 (2) (Leu=leucinato and o - phen=1,10-phenanthroline), have been determined by X-ray diffraction. In each complex, the copper atom is coordinated in distorted squarepyramidal geometry by the bidentate Leu and o - phen ligands at the equatorial sites and water at an axial position. The isopropyl side chain of each Leu extends away from the aromatic ring system of o - phen, thus there is no intramolecular ligand-ligand interaction between them [109]. Compound Coordination number Ref. bis(L-Leucinato) copper(ii) 4 [109] Aqua-(L-leucinato-N,O)-(1,10-phenanthroline-N,N')-copper(ii) nitrate and Aqua-(DL-leucinato- N,O)-(1,10-phenanthroline-N,N')-copper(ii) nitrate
5 [110]
Aqua-(DL-leucinato)-(1,10-phenanthroline)-copper(ii) nitrate 5 [111] II. 8. ASPARTATE Crystal structure of (L-aspartate)(imidazole)copper (II) dehydrate has been investigated.The copper atom shows a distorted square-pyramidal environment being linked to three different aspartate ions (one acting as bidentate ligand through the N(amino) and O(carboxylate) and the other as monodentate through the O of different carboxylate groups) and one imidazole molecule [112]. In the complex, {[Cu(C 4 H 5 O 4 N)(C 10 H 9 N 3 )]·H 2 O} n , the Cu atom has a distorted CuO 2 N 3 square-pyramidal geometry formed by an N , O - bidentate aspartate (asp) anion and an N , N - bidentate 2,2'- bipyridylamine (bpa) molecule in the basal positions, and an O - monodentate asp ligand in the apical site. The complex forms a polymeric chain in which each metal centre is bridged to the next one by the asp anion [113]. Compound Coordination number Ref. catena(L-Aspartate-imidazole-copper(ii)) dihydrate 5 [112] catena-((m2-L-aspartate-N,O,O')-(2,2'-bipyridylamine-N,N')-copper(ii)monohydrate) 5 [113]
II. 9. PHENYLALANINE
For system Cu (L-Phe)(DA) [L-Phe; L-phenylalanine and DA = 2,2‘-bipyridine (bpy) or 1,10-phenanthroline (phen)] the difference absorption spectra in the region 320−400 nm exhibited a peak assignable to the charge transfer interaction between the aromatic rings of DA and L-Phe. The structures of [Cu (L-Phe)(phen)]Cl·3H 2 O and [Cu(L- Phe)(bpy)]ClO 4 ·H 2 O were determined by the X-ray diffraction method. The complexes have a similar distorted square-pyramidal structure around the central Cu (II) ion [114]. Compound Coordination number Ref. Aqua-(1,10-phenanthroline-N,N')-(L-phenylalanine-N,O)-copper(ii) nitratemonohydrate 5 [114] Chloro-(1,10-phenanthroline-N.N')-L-phenylalanine-copper(ii) trihydrate and Aqua-2,2'-bipyridine- L-phenylalanine-copper(ii) perchlorate monohydrate
5 [115]
bis((S,S)-N,N'-bis(2,5-Dimethoxybenzyl)cyclohexane-1,2-diamine)-(Dphenylalanine)- (trifluoromethanesulfonato)-copper(ii) N,N'-bis(2,5-dimethoxybenzyl)cyclohexane-1,2- diammoniumbis(trifluoromethanesulfonate) cyclohexane solvate
5 [116]
Aqua-(1,10-phenanthroline-5,6-dione)-(L-phenylalanine)-copper(ii)perchlorate monohydrate 5 [117] II.10. VALINE The X-ray crystal and molecular structures of trans bis(L-valinato)copper(II) and cis aquabis(L-valinato)copper(II) are presented. Heating of polycrystalline cis aquabis(L-valinato)copper(II) at 90 °C resulted in a dehydrated powder. Recrystallization from aqueous solution of the obtained product yielded anhydrous trans bis(L-valinato)copper(II) [130]. A Novel copper (II) complexe [Cu (L-val)(pmdt)]ClO 4 (L-val = L-valinate ion, and pmdt = N,N,N′,N″,N″ - pentamethyldiethylenetriamine) has been synthesized. The complexes take on a trans ( Oamino acid, Ncentral of pmdt) form, and their CuN 4 O core geometries are approximately regular trigonal bipyramidal, which is novel for copper (II) complexes containing a discrete amino acid chelate ring [118]. Compound Coordination number Ref. cis-aqua-bis((S)-valinato)-copper(ii) 5 [118] (N,N,N',N'',N''-Pentamethyldiethylenetriamine)-(L-valinato)-copper(ii)perchlorate 5 [119] aqua-(L-valinato)-(2,2'-bipyridyl)-copper(ii) nitrate dehydrate and (nitrato)-(L-valinato)-(1,10- phenanthroline)-copper(ii) dihydrate
5 [120]
Aqua-bis(L-valinato)-copper(ii) 5 [121] Aqua-bis(L-valinato)-copper(ii) 5 [122] Aqua-bis(L-valinato-N,O)-copper(ii) 5 [123] catena-((m2-valinato)-(2,2-bipyridyl)-copper(ii) perchlorate monohydrate) 5 [124] catena-(bis(m2-L-valinato)-(m2-4,4'-bipyridine)-diaqua-di-copper(ii)dinitrate) 5 [125] (m2-4,4'-Bipyridine-N,N')-diaqua-bis((4,4'-bipyridine-N)-(L-valinato-N,O))-di-copper(ii) dinitrate dihydrate
5 [126]
Aqua-(1,10-phenanthroline)-(L-valinato)-copper(ii) chloridemonohydrate 5 [127] Aqua-(1,10-phenanthroline)-(valinato)-copper(ii) nitrate dihydrate 5 [128] catena-(trans-bis(m2-(S)-valinato)-copper(ii)) 6 [129] II.1 1. TYROSINE The structure [Cu (L-Tyr)(phen)]ClO 4 ·2.5H 2 O, isolated as crystals, was determined by the X-ray diffraction method. The ternary copper (II) complex [Cu(L- Tyr)(DA)] (L-Try=L-Tyrosin, DA = 2,2‘-bipyridine (bpy) or 1,10- phenanthroline (phen) have been investigated. The difference absorption spectra in the region 3 20 −400 nm exhibited a peak assignable to the charge transfer interaction between the aromatic rings of DA and L- Tyr. the complexe has a similar distorted square-pyramidal structure around the central Cu(II) ion [143]. Compound Coordination number Ref. Aqua-(1,10-phenanthroline-N,N')-L-tyrosine-copper(ii) perchloratesesquihydrate 5 [130] Aqua-(1,4,8,9-tetra-azatriphenylene-N,N')-(L-tyrosine-N,O)-copper(ii)perchlorate monohydrate 5 [131]
II.16. SERINE
Compound Coordination number Ref. D,L:L,D-(2-Amino- 3 - hydroxypropanoato)-(2-aminobutanoato)-copper(ii) 4 [140] (D)- 2 - Amino- 3 - hydroxypropanoato)-((L)- 2 - aminobutanoato)-copper(ii) 4 [141] D-Serine-L-serine-copper(ii) 4 [142] II.17. PROLINE Compound Coordination number Ref. Aqua-(L-proline-L-alanine)-copper(ii) sesquihydrate 4 [143] III. CONCLUSION Amino acids are very important molecules made from amine (-NH 2 ) and carboxylic acid (-COOH) functional groups, with a side-chain specific to each amino acid. About 500 amino acids are known which can be classified in the functional groups' locations as alpha- (α-), beta- (β-), gamma- (γ-) or delta- (δ-) amino acids. Amino acids also perform critical biological roles including neurotransmitters, transport, and in synthesis. 20 of the 22 proteinogenic amino acids are called standard amino acids-those found in human beings. This review gives an overview on structures and Coordination chemistry of copper complexes with 17 of the 20 standard amino acids. A comprehensive review, >120 references, on copper complexes of the amino acids is presented. ACKNOWLEDGEMENTS Support of this work by the Payame Noor University is gratefully acknowledged. REFERENCES [ 1 ] E. A. Lewis, W. B. Tolman. Reactivity of Dioxygen-Copper Systems. Chemical Reviews. 104 (2): 1047–1076 , 2004. [ 2 ] M. R. McDonald, F. C. Fredericks, D. W. Margerum. Characterization of Copper(III)-Tetrapeptide Complexes with Histidine as the Third Residue. Inorganic Chemistry. 36 (14): 3119–3124, 1997. [ 3 ] Q. Wang, AR. Parrish, L. Wang. Expanding the genetic code for biological studies. Chem. Biol. 16 (3): 323–336, 2009. [ 4 ] P. Newsholme, L. Stenson, M. Sulvucci, R. Sumayao, M. Krause. Amino Acid Metabolism. Comprehensive Biotechnology (Second Edition). 1: 3-14, 2011, [ 5 ] http://www.chemguide.co.uk/organicprops/aminoacids/background.html - INTRODUCING AMINO ACIDS [ 6 ] G.J. Jackson, N. glaseri. Essential amino acids, Experimental Parasitology. 34: 111-114,1973. [ 7 ] K. Uchida. Balanced amino acid composition essential for infusion-induced egg development in the mosquito (Culex pipiens pallens). Journal of Insect Physiology.39: 615-621, 1993. [ 8 ] G. H. Anderson, S. Luo, L. T. Ng, E. T. S. Li. Non-essential amino acid and short-term food intake of rats. Nutrition Research. 14( 8): 1179 - 1189, 1994. [ 9 ] M. Hakimi, H. Vahedi, M.Rezvaninezhad, E. Schuh, F. Mohr.Synthesis and characterization of copper(I) complexes from triphenylphosphine and isatin Schiff bases of semi- and thiosemicarbazide. J. Sulfur Chem. 32 (1): 55-61, 2011. [ 10 ] M. Hakimi, K. Moeini, Z. Mardani, M. A. Fernandes, F. Mohr, E. Schuh. Template-direct synthesis of macrocyclic copper(II) complexes of diazacyclam ligand, 1,3,6,10,12,15-hexaazatricyclo[13.3.1.16,10]eicosane. J. Coord. Chem. 65(7): 1232-1245, 2012. [ 11 ] H. An, Y. Guo, Y. Li, E. Wang, J. Lu, L. Xu, C. Hu .Inorg.Chem.Commun. ,7:521, 2004. [ 12 ] X. Y. Jiang, X. Y. Wu, R. M. Yu, D. Q. Yuan, W. Z. Chen. Inorg.Chem.Commun. ,14:1546, 2011. [ 13 ] L.Klistincova, E.Rakovsky, P.Schwendt, G.Plesch,R.Gyepes .Inorg.Chem.Commun. ,13:1275, 2010. [ 14 ] M.Yodoshi, M.Odoko, N.Okabe .Acta Crystallogr.,Sect.E:Struct.Rep.Online ,61:2299, 2005. [ 15 ] B.M.Casari, A.H.Mahmoudkhani, V.Langer .Acta Crystallogr.,Sect.E:Struct.Rep.Online ,60:1949, 2004. [ 16 ] M.Bakir, S.A.Clarke, I.Hassan, R.J.Lancashire,M.Singh-Wilmot .Acta Crystallogr.,Sect.E:Struct.Rep.Online .60:868, 2004. [ 17 ] S.Das, C.Madhavaiah, S.Verma, P.K.Bharadwaj .Inorg.Chim.Acta .358:3236, 2005. [ 18 ] H.C.Freeman, M.R.Snow, I.Nitta, K.Tomita .Acta Crystallogr. 17:1463, 1964. [ 19 ] X.Solans, L.Ruiz-Ramirez, A.Martinez, L.Gasque,J.L.Brianso .Acta Crystallogr.,Sect.C:Cryst.Struct.Commun. 44: 628, 1988. [ 20 ] X.Solans, L.Ruiz-Ramirez, A.Martinez, L.Gasque,R.Moreno-Esparza .Acta Crystallogr.,Sect.C:Cryst.Struct.Commun. 49: 890, 1993.
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