Search results for "Coordination sphere"
showing 10 items of 99 documents
The odd association of a C3h trisamidinium cation and tosylate anion with a series of linear oxalate-bridged trinuclear heterometallic complexes
2013
A series of six isostructural heterometallic trinuclear oxalate-bridged complexes of the formula (TDbenz)(2)(TsO)(2)[M(II)(H(2)O)(2){(μ-ox)M(III)(ox)(2)}(2)]·6H(2)O·2CH(3)OH (TDbenz = 1,3,5-tris[2-(1,3-diazolinium)]benzene; TsO = 4-methylbenzenesulfonate; ox = oxalate; M(III) = Fe, M(II) = Mn (1), Fe (2), Co (3); M(III) = Cr, M(II) = Mn (4), Fe (5), Co (6)) have been synthesized from (NH(4))(3)[M(III)(ox)(3)]·3H(2)O, the chloride salts of the divalent metal ions and the tosylate salt of 1,3,5-tris[2-(1,3-diazolinium)]benzene (trisamidinium). Whereas the crystal structures of compounds 2, 3, 4 and 5 have been investigated by single-crystal X-ray diffraction, the structures of 1 and 6 have be…
Syntheses and Structures of a Series of Acyclic Diaminocarbene Palladium(II) Complexes Derived from 3,4-Diaryl-1H-pyrrol-2,5-diimines and Bisisocyani…
2018
Reactions of 3,4-diaryl-1H-pyrrol-2,5-diimines with various bisisocyanide palladium(II) complexes were studied. The coupling proceeds with one isocyanide ligand to accomplish the acyclic diaminocarbene complexes. The structure of generated diaminocarbene complexes depends on bulkiness of isocyanide ligand in the bisisocyanide complexes of palladium(II). The imino-group of 3,4-diaryl-1H-pyrrol-2,5-diimine reacts with one isocyanide ligand of cis-[PdCl2(CN–R)2] (R = i-Pr, Cy, t-Bu, Bn), and the nitrogen atom of the pyrrole ring is coordinated to the palladium center as the second isocyanide ligand remains intact. In the case of cis-[PdCl2(CN–R)2] (R = 2-acyloxyphenyl, 2-sulfonyloxyphenyl), on…
Cyanocarbanion-based spin-crossover materials: photocrystallographic and photomagnetic studies of a new iron(II) neutral chain
2010
International audience; A new iron(II) chain of formula [Fe(abpt)(2)(tcpd)] [1; (tcpd)(2-) = [C(10)N(6)](2-) = (C[C(CN)(2)](3))(2-) = 2-dicyanomethylene-1,1,3,3-tetracyanopropanediide anion, abpt = 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole] has been synthesized and characterized by IR spectroscopy, detailed variable-temperature single-crystal X-ray diffraction, magnetic and photomagnetic measurements. The crystal structure determination of 1 reveals a one-dimensional structural architecture in which the (tcpd)(2-) cyanocarbanion acts as a μ(2)-bridging ligand and the two abpt molecules act as chelating ligands. Detailed X-ray diffraction studies as a function of the temperature (293-10 K…
Versatility and dynamics of the copper(I) coordination sphere in sterically hindering tris(pyrazolyl)methane-incorporating macrobicycles
2009
Two arene-capped macrobicycles (1 and 2) incorporating the tris(pyrazolyl)methane (Tpm) chelate have been prepared from a benzylthiol-functionalized Tpm precursor (3). Reaction of either macrobicycle with Cu(CH3CN)4+ leads to tetrahedral or trigonal-planar, fluxional complexes incorporating the Cu(CH3CN)+ subunit ([Cu(1)(CH3CN)]+ and [Cu(2)(CH3CN)]+). The acetonitrile ancillary ligand does not fit inside the macrobicycle cavity and can be removed by heating under vacuum, which produces the [Cu(1)]+ and [Cu(2)]+ species probably involving intramolecular thioether coordination. The [Cu(1)(CH3CN)]+ complex was shown to convert slowly in wet acetone into a helical coordination polymer, which is…
Synthesis and characterization of vanadyl(IV) complexes of Schiff bases derived from anthranilic acid and salicylaldehyde (or its derivatives) or ace…
1997
Anhydrous, dimeric vanadyl(IV) complexes of Schiff bases derived from [1+1] condensation of salicylaldehyde (or its derivatives) and anthranilic acid, have been synthesized from CH3CN and were characterized by elemental analysis, FTIR, EPR, absorption, TGA, cyclic voltammetry and room temperature magnetic susceptibility measurements. These complexes were found to be oxidized by air in polar solvents like MeOH and DMF to V-V products. The E(1/2) values were found to be around 660 mV indicating that the carboxylate group favours vanadyl(IV) binding when compared to the alkoxo-bound vanadium complexes. Oxidative instability of these complexes are dependent on the substituent on the salicylalde…
Zn(II)-alloferon complexes - Similar sequence, different coordination modes, no antibacterial activity.
2020
Often, in the search for a highly defined scientific phenomenon, a different one becomes apparent. This was also the case of this work, in the scope of which we planned to search for metal-enhanced, novel antibacterial/ antifungal compounds. Instead, we denied the existence of such and revealed the details of the bioinorganic chemistry of Zn(II)-alloferon complexes. Zinc(II) complexes of alloferon 1 and 2, ligands with a sequential difference of one amino acid only, show a substantially different coordination pattern at physiological pH. In the case of Zn(II)-alloferon 1 species, a histamine-like binding mode is observed (N-terminal amine and imidazole of His-1) and the coordination sphere …
Rational design of aminoanthraquinones for colorimetric detection of heavy metal ions in aqueous solution
2011
A family of water-soluble colorimetric chemosensors incorporating an anthraquinone signalling subunit functionalized with a polyamine chain that bears hydrophilic diethoxyphosphoryl moieties was prepared with the aim of assaying metal cations. The outstanding UV-Vis absorption properties of the 1-aminoanthraquinone chromophore allowed the efficient visual detection and quantification of copper(II) ions by chelators L(1)-L(3) in buffered aqueous solution. Moreover, the visible response of L(2) is not interfered by addition of large excesses of 13 common metal ions, whereas chemosensor L(3) produces also a color change in the presence of equimolar amounts of lead(II). Considering the 134 nm g…
A Two-State Computational Investigation of Methane C-H and Ethane C-C Oxidative Addition to [CpM(PH3)]n+ (M=Co, Rh, Ir;n=0, 1)
2006
Reductive elimination of methane from methyl hydride half-sandwich phosphane complexes of the Group 9 metals has been investigated by DFT calculations on the model system [CpM(PH(3))(CH(3))(H)] (M = Co, Rh, Ir). For each metal, the unsaturated product has a triplet ground state; thus, spin crossover occurs during the reaction. All relevant stationary points on the two potential energy surfaces (PES) and the minimum energy crossing point (MECP) were optimized. Spin crossover occurs very near the sigma-CH(4) complex local minimum for the Co system, whereas the heavier Rh and Ir systems remain in the singlet state until the CH(4) molecule is almost completely expelled from the metal coordinati…
Copper(II) complexes of 1,4,5,8,9,12-hexaazatriphenylene with oxalate, squarate, perchlorate as auxiliary ligands or counter ion
2002
Abstract The crystal structures of [Cu(hat)(H2O)(ox)]·H2O (I), [Cu(hat)(H2O)3(sq)]·3H2O (II) and [Cu(hat)(H2O)2](ClO4)2·4H2O (III) have been determined from X-ray single crystal diffraction data (hat=1,4,5,8,9,12-hexaazatriphenylene, ox=oxalate, sq=squarate=dianion of 3,4-dihydroxy-cyclobut-3-ene-1,2-dione). Compound I crystallises in the triclinic system, space group P 1 with a=6.6626(10), b=9.2001(14), c=12.9954(19) A , α=103.301(15), β=91.414(21), γ=105.523(13)°, Z=2; compound II in the orthorhombic system, space group P212121 with a=6.9274(2), b=8.4327(3), c=34.0577(14) A , Z=4; and compound III in the monoclinic system, space group C2/c with a=22.6652(10), b=9.2220(10), c=16.1400(10) A…
Investigation into the reactivity of oxoniobocene complexes [Cp*2Nb(O)R] (Cp*=η5-C5Me5; R=H, OH, OMe) towards heterocumulenes: formation of carbamat…
2001
Abstract The reaction of [Cp*2NbCl2] (Cp*=η5-C5Me5) with KOH or Ba(OH)2·8H2O in THF was investigated under slightly modified conditions. In addition to the known complex [Cp*2Nb(O)H] (1), the new compound [Cp*2Nb(O)OH] (2) was formed. The reaction of 2 with PhNCS gave yellow [Cp*2Nb(O){SC(O)NHPh}] (3), while PhNCO formed yellow [Cp*2Nb(O){OC(O)NHPh}] (4). Complexes 3 and 4 were analytically and spectroscopically characterized. X-ray diffraction analyses of both compounds show that they contain either η1-S-thiocarbamato (3) or η1-O-carbamato ligand (4) along with a terminal NbO group. The reaction of 1 with one equivalent of PhNCO mainly gave orange [Cp*2NbH{OC(O)NPh}] (5) along with so…