scholarly journals Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond

Inorganics ◽  
2021 ◽  
Vol 9 (9) ◽  
pp. 70
Author(s):  
Graeme Hogarth ◽  
Damian C. Onwudiwe

Copper dithiocarbamate complexes have been known for ca. 120 years and find relevance in biology and medicine, especially as anticancer agents and applications in materials science as a single-source precursor (SSPs) to nanoscale copper sulfides. Dithiocarbamates support Cu(I), Cu(II) and Cu(III) and show a rich and diverse coordination chemistry. Homoleptic [Cu(S2CNR2)2] are most common, being known for hundreds of substituents. All contain a Cu(II) centre, being either monomeric (distorted square planar) or dimeric (distorted trigonal bipyramidal) in the solid state, the latter being held together by intermolecular C···S interactions. Their d9 electronic configuration renders them paramagnetic and thus readily detected by electron paramagnetic resonance (EPR) spectroscopy. Reaction with a range of oxidants affords d8 Cu(III) complexes, [Cu(S2CNR2)2][X], in which copper remains in a square-planar geometry, but Cu–S bonds shorten by ca. 0.1 Å. These show a wide range of different structural motifs in the solid-state, varying with changes in anion and dithiocarbamate substituents. Cu(I) complexes, [Cu(S2CNR2)2]−, are (briefly) accessible in an electrochemical cell, and the only stable example is recently reported [Cu(S2CNH2)2][NH4]·H2O. Others readily lose a dithiocarbamate and the d10 centres can either be trapped with other coordinating ligands, especially phosphines, or form clusters with tetrahedral [Cu(μ3-S2CNR2)]4 being most common. Over the past decade, a wide range of Cu(I) dithiocarbamate clusters have been prepared and structurally characterised with nuclearities of 3–28, especially exciting being those with interstitial hydride and/or acetylide co-ligands. A range of mixed-valence Cu(I)–Cu(II) and Cu(II)–Cu(III) complexes are known, many of which show novel physical properties, and one Cu(I)–Cu(II)–Cu(III) species has been reported. Copper dithiocarbamates have been widely used as SSPs to nanoscale copper sulfides, allowing control over the phase, particle size and morphology of nanomaterials, and thus giving access to materials with tuneable physical properties. The identification of copper in a range of neurological diseases and the use of disulfiram as a drug for over 50 years makes understanding of the biological formation and action of [Cu(S2CNEt2)2] especially important. Furthermore, the finding that it and related Cu(II) dithiocarbamates are active anticancer agents has pushed them to the fore in studies of metal-based biomedicines.

2014 ◽  
Vol 43 (14) ◽  
pp. 5409-5426 ◽  
Author(s):  
Athanassios C. Tsipis ◽  
Ioannis N. Karapetsas

Exhaustive benchmark DFT calculations reveal that the non-relativistic GIAO-PBE0/SARC-ZORA(Pt)∪6-31+G(d)(E) computational protocol predicts accurate 195Pt NMR chemical shifts for a wide range of square planar Pt(ii) and octahedral Pt(iv) anticancer agents.


2006 ◽  
Vol 62 (7) ◽  
pp. m1705-m1707 ◽  
Author(s):  
Gideon Steyl ◽  
Leo Kirsten ◽  
Andreas Roodt

The centrosymmetric title compound, [PdCl2(C19H17P)2], crystallizes with a square-planar geometry about the PdII metal centre. The most important bond distances include Pd—P (trans P) of 2.3404 (9) Å and Pd—Cl (trans Cl) of 2.2977 (12) Å. Weak intra- and intermolecular hydrogen bonding is observed in the solid-state structure between the chloro and phenyl H atoms. This weak intermolecular hydrogen-bonding pattern forms a one-dimensional chain along the b axis.


1982 ◽  
Vol 37 (3) ◽  
pp. 332-340 ◽  
Author(s):  
Thomas Gerdau ◽  
Reinhard Kramolowsky

Abstract The preparation and structural characterization of phosphinomethylthioethernickel(II) complexes of the general type [NiX2(Ph2PCH2SR)2] (X = CI, Br, I, NCS: R = Me, Ph) are reported. In all the complexes the phosphinomethylthioethers act as monodentate ligands coordinating via the phosphorus atom. The isothiocyanate complexes are diamagnetic both in solution and in the solid state and have been assigned trans-planar configuration. As shown by magnetic measurements and by electronic spectroscopy, the halo complexes exhibit a square-planar (diamagnetic) ⇄ distorted-tetrahedral (paramagnetic) equilibrium in solution, while in the solid state the complexes are either square-planar or distorted-tetrahedral. For the complex [NiBr2(Ph2PCH2SMe)2] both isomers have been isolated in the solid state.


Molecules ◽  
2021 ◽  
Vol 26 (9) ◽  
pp. 2460
Author(s):  
Melvyn B. Ansell ◽  
George E. Kostakis ◽  
Oscar Navarro ◽  
John Spencer

The stoichiometric reaction of cis-[Pd(ITMe)2(SiR3)2], where (SiR3 = SiMe3 and SiMe2Ph and ITMe = 1,3,4,5-tetramethylimidazol-2-ylidene) with allyl bromide affords the corresponding allylsilanes along with complexes of the type trans-[Pd(ITMe)2(SiR3)(Br)]. The structure of trans-[Pd(ITMe)2(SiMe2Ph)Br] 2b has been determined in the solid state and displays a slightly distorted square-planar geometry with the two N-heterocyclic carbene ligands in a trans-configuration.


1999 ◽  
Vol 54 (10) ◽  
pp. 1235-1243 ◽  
Author(s):  
Joachim Heinicke ◽  
Attila Dal ◽  
Hans-Friedrich Klein ◽  
Olaf Hetche ◽  
Ulrich Flörke ◽  
...  

o-Phosphinophenols 1 (P⌒OH ) react with equimolar amounts of Ni(PMe3)4 at low temperatures to give yellow Ni(0) complexes such as [(HO∼P)Ni(PMe3)3] 2a with only P coordination of the P⌒OH ligand. Oxidation of solutions of 1 and Ni(PMe3)4 by dioxygen leads to brown bis(o-phosphinophenolato-P⌒O)nickel chelate complexes 3a-d. Structure elucidation by NMR is consistent with a cis-square planar geometry for 3a-c and a trans-square planar solution structure of the tert-butylphenylphosphino derivative 3d. The geometric isomers were distinguished by different ranges of phosphorus coordination shifts and 31P-13C-2 and 31P-13C-1 coupling constants. In the solid state, 3d adopts also a cis-square planar geometry. The steric stress of the substituents causes anti-orientation of the tert-butyl groups at phosphorus (R,R and S,S diastereoisomers) and a significant distorsion (22°) of the planes of the two five-membered rings. With less bulky substituents the R,S and S,R diastereoisomers are preferred as in the cis-square planar complex 3c with syn-orientation of the two isopropyl and phenyl groups, respectively.


2020 ◽  
Vol 22 (36) ◽  
pp. 20349-20361
Author(s):  
Haley L. Swanson ◽  
Chengchen Guo ◽  
Michael Cao ◽  
J. Bennett Addison ◽  
Gregory P. Holland

Silica nanoparticles can be designed to exhibit a diverse range of morphologies (e.g. non-porous, mesoporous), physical properties (e.g. hydrophobic, hydrophilic) and a wide range of chemical and biomolecular surface functionalizations.


Author(s):  
John A. Tossell ◽  
David J. Vaughan

This work is based on the observation that further major advances in geochemistry, particularly in understanding the rules that govern the ways in which elements come together to form minerals and rocks, will require the application of the theories of quantum mechanics. The book therefore outlines this theoretical background and discusses the models used to describe bonding in geochemical systems. It is the first book to describe and critically review the application of quantum mechanical theories to minerals and geochemical systems. The book consolidates valuable findings from chemistry and materials science as well as mineralogy and geochemistry, and the presentation has relevance to professionals in a wide range of disciplines. Experimental techniques are surveyed, but the emphasis is on applying theoretical tools to various groups of minerals: the oxides, silicates, carbonates, borates, and sulfides. Other topics dealt with in depth include structure, stereochemistry, bond strengths and stabilities of minerals, various physical properties, and the overall geochemical distribution of the elements.


1993 ◽  
Vol 329 ◽  
Author(s):  
Michael Canva ◽  
Patrick Georges ◽  
Jean-Fran^ois Perelgritz ◽  
Alain Brun ◽  
Fréddric Chaput ◽  
...  

AbstractPhotoresistant laser dyes were trapped in silica based xerogel host matrices to obtain solid state tunable lasers. For this purpose very dense xerogel samples with improved chemical and physical properties were prepared at room temperature by the sol-gel technology. The as-prepared materials were polished to obtain optical quality surfaces and were used as new lasing media.Lasing action of such different dyes as rhodamine, perylene and pyrromethene doping dense sol-gel matrices was demonstrated. Efficiencies of 30 % or lifetimes of more than 100,000 shots were achieved with different new ≤dye dopant/host matrix≥ couples. Their different performances are reviewed and discussed.


Alloy Digest ◽  
1982 ◽  
Vol 31 (8) ◽  

Abstract ANACONDA Alloy 268 is a copper-zinc alloy with excellent cold-working properties; it can be cold worked by all the conventional fabrication processes. Its corrosion resistance is excellent-to-good in most environments. This alloy has a wide range of applications including items such as springs, bathroom fixtures, automotive radiators, lamp sockets and sanitary traps. This datasheet provides information on composition, physical properties, hardness, elasticity, and tensile properties as well as fatigue. It also includes information on corrosion resistance as well as forming, heat treating, machining, and joining. Filing Code: Cu-442. Producer or source: Anaconda American Brass Company.


Alloy Digest ◽  
1981 ◽  
Vol 30 (8) ◽  

Abstract CENTRI-CAST GRAY IRON 50 is a centrifugally cast gray iron with a nominal tensile strength of 50,000 psi. It is cast in the form of tubing which has a wide range of uses in applications where size and shape are of paramount importance and freedom from pattern cost is an important consideration. Among its many applications are farm machinery, seals, bushings, machine tools and general machinery uses. This datasheet provides information on composition, physical properties, microstructure, hardness, elasticity, tensile properties, and compressive and shear strength as well as fatigue. It also includes information on casting, heat treating, machining, and surface treatment. Filing Code: CI-51. Producer or source: Federal Bronze Products Inc..


Sign in / Sign up

Export Citation Format

Share Document