Transition metal quinone–thiosemicarbazone complexes 1: Evaluation of EPR covalency parameters and redox properties of pseudo-square-planar copper(II)–naphthoquinone thiosemicarbazones

Polyhedron ◽  
2005 ◽  
Vol 24 (8) ◽  
pp. 889-899 ◽  
Author(s):  
Rajeev C. Chikate ◽  
Avadhoot R. Belapure ◽  
Subhash B. Padhye ◽  
Douglas X. West
1994 ◽  
Vol 346 ◽  
Author(s):  
Andrew B. Bocarsly ◽  
Gireesh Kumar ◽  
Marija Heibel

ABSTRACTThe reaction of a wide variety of cyanometalate complexes of the general form [M(CN)x]n- (where M= a transition metal ion) with square planar [PdCl4]2- in aqueous solution leads to the formation of linear polymers. Polymerization occurs via substitution of chloride ligands on the Pd(II) centers, by the nitrogen end of the cyanide ligand to generate extended bridging cyanide structures. Upon generation at room temperature polymer solutions of this type under go a sol-gel transition to generate robust hydrogels having water content in excess of 95%. In the case of the cyanocobaltate/tetrachloropalladate gel, pyrolysis at 900°C produces ferromagnetic Pd/Co metallic alloys having novel morphological character. Materials formed with a hydrogel having a 2:1 Pd to Co stoichiometry are found to be “sponge-like”. When placed in water, the metallic matrix swells becoming pliable and holding up to seven equivalents of water per metal site. The conductivity and magnetic properties of this material are maintained in the swollen state. Sintering of the Pd/Co hydrogel in air generates the layered oxide, PbCoO2 having a delafossite structure.


2013 ◽  
Vol 68 (5-6) ◽  
pp. 458-466 ◽  
Author(s):  
Iris Klawitter ◽  
Steffen Meyer ◽  
Serhiy Demeshko ◽  
Franc Meyer

Two methylene-bridged bis(imidazolium) salts [H4L1](PF6)2 and [H4L2](PF6)2 with appended amide groups have been synthesized which, after deprotonation, may serve as potentially tetradentate ligands providing two bis(imidazole-2-ylidene) and two amide donors. Using [H4L1](PF6)2, a square-planar nickel(II) complex [NiL1] and a six-coordinate bis(ligand) iron(II) complex [Fe(HL1)2] have been isolated and structurally characterized. Their low-spin states have been confirmed spectroscopically, and their redox properties have been studied by cyclic voltammetry. Oxidations are metal-centered to give NiIII and FeIII species, respectively


2017 ◽  
Vol 19 (43) ◽  
pp. 29068-29076 ◽  
Author(s):  
Yu-Te Chan ◽  
Ming-Kang Tsai

The CO2 reduction capabilities of transition-metal-chelated nitrogen-substituted carbon nanotube models (TM-4N2v-CNT, TM = Fe, Ru, Os, Co, Rh, Ir, Ni, Pt or Cu) are characterized by density functional theory.


2007 ◽  
Vol 62 (9) ◽  
pp. 1133-1138 ◽  
Author(s):  
Veli T. Kasumov ◽  
Ibrahim Uçar ◽  
Ahmet Bulut ◽  
Fevzi Kösal

The coordination chemistry of N-(2,6-di-methylphenyl)-2-hydroxy-3-methoxybenzaldimine (1) with Cu(II) has been investigated by X-ray crystallography, electronic and EPR spectroscopies, as well as by electro- and magnetochemistry. The title complex 2 crystallizes in the orthorhombic space group P212121 (a = 8.1538, b = 17.7466, c =19.8507 Å). The mononuclear square-planar molecules 2 featuring trans-N2O2 coordination are connected via weak intermolecular C-H· · ·π interactions into infinite chains parallel to the a axis. Although the intermolecular Cu· · ·Cu separations within individual chains and between chains are very long (8.154 and 9.726 Å ), the exchange interaction parameter G = 2.03 < 4, estimated from solid state EPR spectra, suggests the existence of long-distance superexchange pathways between adjacent Cu(II) centers. The electronic and electrochemical features of the compound are also discussed.


1991 ◽  
Vol 46 (12) ◽  
pp. 1601-1608 ◽  
Author(s):  
Dieter Sellmann ◽  
Stefan Fünfgelder ◽  
Falk Knoch ◽  
Matthias Moll

In order to elucidate specific properties of nickel sulfur complexes, redox and addition-elimination reactions of [Ni(′OS4')]2, [Ni(′NHS4')]2, [Ni(′S5')], [Ni('S4—C5')], and [Ni('S4—C3')] were investigated ('OS4′ 2' = 2,2'-bis(2-mercaptophenylthio)diethylether(2—), 'NHS4'2- = 2,2'-bis(2-mercaptophenylthio)diethylamine(2—), 'S5'2- = 2,2'-bis(2-mercaptophenylthio)diethylsulfide(2—), 'S4-C5'2- = 1,5-bis(2-mercaptophenylthio)pentane(2—), 'S4—C3'2- = 1,3-bis(2-mercaptophenylthio)propane(2—)).Cyclovoltammetry proves the complexes to be redox inactive between —1.4 and +0.8 V vs. NHE. Above +0.8 V the complexes are irreversibly oxidized, below —1,4 V desalkylation takes place and [Ni(′S,′)2]2- is formed. An X-ray structure analysis was carried out of (NMe4)2[Ni(′S2')2], which shows a planar anion with the Ni center in a nearly perfect square planar coordination. Distances and angles are practically identical to those in the [Ni(′S2')2-] monoanion.The complexes coordinate only phosphines as coligands, but thioether donors simultaneously decoordinate and, dependant of reaction temperature, mono- or trisphosphine complexes are formed. [Ni(′S4—C3')(PMe3)] was characterized by X-ray structure analysis and exhibits a square pyramidal coordination geometry.


2012 ◽  
Vol 10 (6) ◽  
pp. 1709-1759 ◽  
Author(s):  
Milan Melnik ◽  
Ondrej Sprusansky ◽  
Clive Holloway

AbstractThis review covers almost two hundred and twenty heterobinuclear platinum compounds in which Pt⋯M separation is over 3.0 Å. The M is a transition metal (Cu, Ag, Au, Ti, V, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni and Pd). There is an example of a lanthanide, Yb and a actinide, U. The Pt atom has oxidation numbers 0, +2 and +4. The Pt coordination geometries include trigonal planar Pt(0); square planar Pt(II); trigonal bipyramidal, and pseudo octahedral Pt(IV), with the most frequent being square planar. The most common ligands for Pt are P and C donor atoms, as well as a chlorine atom. The Pt — Ag distance of 3.002(1) Å is the shortest found in this series. There are examples which contain two crystallographically independent molecules, which differ mostly by degree of distortion and even one unique example, which contains eight such molecules. These are examples of distortion isomerism. Factors affecting bond lengths and angles are discussed and some ambiguities in coordination polyhedral are outlined.


2011 ◽  
Vol 76 (1) ◽  
pp. 75-83 ◽  
Author(s):  
A.S. Ramasubramanian ◽  
Ramachandra Bhat ◽  
Ramakrishna Dileep ◽  
Sandya Rani

Transition metal complexes of 5-bromosalicylidene-4-amino-3- mercapto-1,2,4-triazine-5-one with metal precursors, such as Cu(II), Ni(II), Co(II) and Pd(II), were synthesized and characterized by physicochemical and spectroscopic techniques. All the complexes are of the ML type. Based on analytical, spectral data and magnetic moments, the Co(II) and Ni(II) complexes were assigned octahedral geometries, while the Cu (II) and Pd(II) complexes square planar. A study on the catalytic oxidation of benzyl alcohol, cyclohexanol, cinnamyl alcohol, 2-propanol and 2- methyl-1-propanol was performed with N-methylmorpholine-N-oxide (NMO) and molecular oxygen as co-oxidants. All the complexes and their parent organic moiety were screened for their biological activity on several pathogenic bacteria and were found to possess appreciable bactericidal properties.


2014 ◽  
Vol 79 (3) ◽  
pp. 291-302 ◽  
Author(s):  
Vukadin Leovac ◽  
Ljiljana Vojinovic-Jesic ◽  
Sonja Ivkovic ◽  
Marko Rodic ◽  
Ljiljana Jovanovic ◽  
...  

The synthesis and structural characterization of a square-planar copper(II) complex with pyridoxal S-methylisothiosemicarbazone (PLITSC) of the formula [Cu(PLITSC?H)H2O]Br?H2O (1) as the first Cu(II) complex with monoanionic form of this ligand were described. Complex 1 together with two previously synthesized complexes [Cu(PLITSC)Br2] (2) and [Cu(PLITSC)Br(MeOH)]Br (3) were characterized by elemental analysis, IR and electronic spectra and also by the methods of thermal analysis, conductometry and magnetochemistry.


1974 ◽  
Vol 96 (13) ◽  
pp. 4121-4125 ◽  
Author(s):  
L. G. Vanquickenborne ◽  
J. Vranckx ◽  
C. Goeller-Walrand

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