0000000000515358
AUTHOR
Julia Jezierska
Stabilities and coordination modes of histidine in copper(II) mixed-ligand complexes with ethylenediamine, diethylenetriamine or N,N,N′,N″,N″-pentamethyldiethylenetriamine in aqueous solution
Abstract Solution equilibrium studies on the Cu(II)–polyamine–methionine ternary systems (polyamine: ethylenediamine (en), diethylenetriamine (dien), N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (Me5dien)) have been performed by pH-potentiometry, UV–Vis spectrophotometry and EPR methods. The obtained results suggest the formation of the mixed-ligand complexes with [Cu(A)(Met)]+ stoichiometry in all studied systems. Our spectroscopic results indicate the tetragonal geometry for [Cu(en)(Met)]+, the geometry slightly deviated from square pyramidal for [Cu(dien)(Met)]+ and strongly deviated from square pyramidal towards trigonal bipyramidal for the [Cu(Me5dien)(Met)]+ species. The coordination …
Stabilities and Coordination Modes of α-Alaninephosphonic Acid in Copper(II) Heteroligand Complexes with Ethylenediamine, Diethylenetriamine or N,N,N′,N′,N″-Pentamethyldiethylene Triamine in Aqueous Solution
Solution equilibrium studies on Cu2+–L1–L2 ternary systems have been performed by pH-potentiometry, UV–Vis spectrophotometry and EPR methods (L1 corresponds to polyamines such as ethylenediamine (en), diethylenetriamine (dien), or N,N,N′,N′,N″-pentamethyldiethylenetriamine (Me5dien) and L2 represents 1-aminoethylphosphonic acid (α-alaninephosphonic acid)). The obtained results suggest the formation of heteroligand complexes with [Cu(L1)(α-Ala(P))] stoichiometry in all studied systems. Additionally, in the system with en the [Cu(en)(α-Ala(P))H−1]− species is formed in basic solution. Our spectroscopic results indicate tetragonal geometry for the [Cu(en)(α-Ala(P))] species, geometry slightly …
Cu2+ Coordination Properties of a 2-Pyridine Heptaamine Tripod: Characterization and Binding Mechanism
The synthesis, protonation, and Cu(2+) coordination chemistry of a tripodal heptaamine ligand (L(1)) functionalized with 2-pyridine fragments at the ends of its three branches are reported. L(1) presents six relatively high protonation constants followed by much more reduced constant that as indicated by the UV-vis and NMR data, occur on the pyridine fragments. p[H]-metric, ESI/MS(+), EPR and UV-vis data show that L(1) is able to form mono-, di-, and trinuclear Cu(2+) complexes. Slippage movements and molecular reorganizations have been observed to occur as a function of p[H] in the 1:1 Cu(2+) complexes. The kinetic studies showed that the complex formation is fast and proceeds through a di…
Unique direct synthesis of cyanide-bridged Fe2Cu2 molecular squares by destruction of sodium nitroprusside
Abstract The one-pot reaction of copper powder, sodium nitroprusside, ammonium thiocyanate and 2,2′-bipyridine (bpy) in acetonitrile solution at ambient conditions of air and water yields the novel heterometallic [Fe2Cu2(bpy)6(μ-CN)4(NCS)2]2[Fe(CN)5(NO)](NCS)2·5H2O complex 1, which has been structurally and magnetically characterized. The most prominent feature of this complex is the unique tetranuclear Fe 2 II Cu 2 II squares comprised [Cu(bpy)NCS]+ and [Fe(bpy)2]2+ corners with CN edges. The Cu⋯Cu and Fe⋯Fe separations are ∼6.72 and ∼7.73 A, respectively. The variable-temperature magnetic susceptibility study revealed that a very weak antiferromagnetic coupling is active between Cu(II) ce…
Supramolecular diversity and magnetic properties of novel heterometallic Cu(II)/Cr(III) complexes prepared from copper powder, Reineckes salt and ethylenediamine
Abstract Three novel heterometallic complexes [Cu(en) 2 Cr(NCS) 4 (NH 3 ) 2 ][Cr(NCS) 4 (NH 3 ) 2 ] · 6dmf ( 1 ), [Cu(en) 2 Cr(NCS) 4 (NH 3 ) 2 ](OAc) ( 2 ) and [{Cu(en) 2 } 3 {Cr(NCS) 4 (NH 3 ) 2 } 2 (NCS) 2 ](NCS) 2 ( 3 ) have been synthesized in a one-pot reaction from copper powder, Reineckes salt, NH 4 X [X − = OAc − ( 2 ), NCS − ( 3 )] in a dmf ( 1 ) or CH 3 CN ( 2 , 3 ) solution of ethylenediamine (en). X-ray studies showed that 1 and 2 consist of cationic polymeric chains, formed by Cu ( en ) 2 2 + and Cr ( NCS ) 4 ( NH 3 ) 2 - building blocks that bridged through thiocyanate anions. In both complexes, distinct hydrogen bonds are present and serve to increase the dimensionality of …
Structural and magnetic studies of tetranuclear heterometallic M/Cr (M = Co, Mn) complexes self-assembled from zerovalent cobalt or manganese, Reineckes salt and diethanolamine
Abstract Four novel heterometallic complexes [Co2Cr2(NCS)4(HDea)2(Dea)2]·4dmf (1), [Co2Cr2(NCS)4(HDea)2(Dea)2]·4dmso (2), [Mn2Cr2(NCS)4(HDea)2(Dea)2(dmf)2]·2dmf (3) and [Mn2Cr2(NCS)4(HDea)2(Dea)2(dmso)2]·4dmso (4) have been prepared using zerovalent cobalt (1, 2) or manganese (3, 4), Reineckes salt, ammonium thiocyanate and a non-aqueous solution of diethanolamine (H2Dea) in air. The single X-ray analysis reveals that all compounds have similar centrosymmetric crystal structures based on a tetranuclear {M2Cr2(μ3-O)2(μ-O)4} (M = Co, Mn) core. Variable-temperature magnetic susceptibility measurements of 1, 2 and 4 show antiferromagnetic coupling between the magnetic centers, while 3 exhibits …
Coordination abilities of l-glutamic acid γ-monohydroxamic acid towards copper(II) in the absence and presence of some aliphatic amines
Abstract Solution equilibrium studies on the Cu 2+ –(A)–(Glu-γ-ha) ternary systems ((A) = polyamine: ethylenediamine (en), diethylenetriamine (dien), N , N , N ′, N ″, N ″-pentamethyldiethylenetriamine (Me 5 dien); (Glu-γ-ha) = l -glutamic-γ-hydroxamic acid) have been performed by pH-potentiometry, UV–Vis spectrophotometry and EPR methods. The obtained results suggest the formation of the heteroligand complexes with [Cu(A)(Glu-γ-ha)] + stoichiometry in all studied systems. Our spectroscopic results indicate the tetragonal geometry for the [Cu(en)(Glu-γ-ha)] + species in which Glu-γ-ha acts as a tridentate ligand, the geometry slightly deviated from square pyramidal for [Cu(dien)(Glu-γ-ha)]…