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Treatment of [Et4N][Tp*WS3] (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) (1) with CuX (X = Br, SCN) and PPh3 or 1,1-bis(diphenylphosphino)methane (dppm) produced two neutral trinuclear clusters [Tp*W(mu3-S)(mu-S)2Cu 2Br(PPh3)] (2) and [Tp*W(mu3-S)(mu-S) 2Cu2(SCN)(dppm)]2·MeCN·Et 2O (3·MeCN·Et2O). Reactions of 1 with [Cu(MeCN)4]PF6, NH4PF6 and 1,3-bis(diphenylphosphino)propane (dppp), N,N-bi(diphenylphosphanylmethyl)-2- aminopyridine (bdppmapy), N,N,N?,N?-tetra(diphenylphosphanylmethyl) ethylenediamine (dppeda), or 1,4-N,N,N?,N?- tetra(diphenylphosphanylmethyl)benzenediamine (dpppda) afforded four clusters containing butterfly-shaped [Tp*WS3Cu2] cores, [Tp*W(mu3-S)(mu-S)2Cu2(dpppds)] (PF6)·1.25MeCN (dpppds = 1,3-bis(diphenylphosphino)propane disulfide) (4·1.25MeCN), [Tp*W(mu3-S)(mu-S) 2Cu2(bdppmapy)](PF6)·3MeCN (5·3MeCN) and {[Tp*W(mu3-S)(mu-S)2Cu 2]2(L)]}(PF6)2·Sol (6·Et2O: L = dppeda, Sol = Et2O; 7·1.25MeCN: L = dpppda, Sol = 1.25MeCN). Compounds 2-7 were characterized by elemental analysis, IR, UV-Vis, 1H and 31P{1H} NMR spectra, electrospray ion mass spectra (ESI-MS) and single-crystal X-ray diffraction. Compound 2 or 3 has a butterfly-shaped [Tp*WS 3Cu2] core in which one [Tp*WS3] unit binds two Cu(i) centers via one mu3-S and two mu-S atoms. In the cationic structure of 4 or 5, one in situ-formed dpppds or bdppmapy combines with the [Tp*WS3Cu2] core via each of its two S atoms or two P atoms coordinated at each Cu(i) center. In the bicationic structure of 6 or 7, two [Tp*WS3Cu2] cores are linked by one dppeda or dpppda bridge to form a bicyclic structure. The isolation of 2-7 with unstable [Tp*WS3Cu2] cores may be ascribed to the coordination of P- or S-donor ligands at Cu(i) centers of these cores. The third-order nonlinear optical (NLO) properties of 2-7 in DMF were also investigated by using the femtosecond degenerate four-wave mixing (DFWM) technique at 800 nm.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

Extracurricular laboratory:new discovery of C10H16CuO4

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Reactions of the Schiff base ligand OH-C6H4-CH[dbnd]NC(CH2OH)3 (H4L) with copper(II) salts in various reaction media afforded complexes [Cu4(H2L)4]·MeOH (1·MeOH), [Cu2(O2CMe)2(H3L)2] (2), [Cu4(H2L)4(H2O)2]·1.5dmf (3·1.5dmf), [Cu4(H2L)4(H2O)]·MeOH (4·MeOH) and [Cu4(H2L)4]2·2H2O·7MeOH (5·2H2O·7MeOH). Compounds 1, 3 and 4 consist of neutral tetranuclear entities in which the CuII ions are coordinated by the tridentate Schiff base ligands, forming a tetranuclear Cu4O4 cubane-like configuration. Compound 5 contains similar cubane-like tetranuclear entities which are further linked through the hydroxyl groups of the ligands thus forming dimers of cubanes. Compound 2 contains a neutral dinuclear entity in which the CuII ions are bridged through the Schiff base and the acetate ligands, comprising distorted Cu2O2 core. The Schiff base ligand adopts five different coordination modes and two deprotonation states in the structures of 1?5 acting simultaneously as chelating and bridging agent between the metal ions. The lattice structures of 1?5 exhibit interesting 3D networks based on hydrogen bonded metal clusters and they are studied with Hirshfeld Surface analysis methods.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

The Shocking Revelation of Cuprous thiocyanate

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The meagre (structurally defined) array of 1:2 silver(I) (pseudo-)halide:unidentate nitrogen base adducts is augmented by the single-crystal X-ray structural characterization of the 1:2 silver(I) thiocyanate:piperidine (‘pip’) adduct. It is of the one-dimensional ‘castellated polymer’ type previously recorded for the chloride: ?Ag(pip) 2(mu-SCN)Ag(pip)2? a single bridging atom (S) linking successive silver atoms. By contrast, in its copper(I) counterpart, also a one-dimensional polymer, the thiocyanate bridges as end-bound SN-ambidentate: ?CuSCNCuSCN? A study of the 1:1 silver(I) bromide:quinoline (‘quin’) adduct is recorded, as the 0.25 quin solvate, isomorphous with its previous reported ‘saddle polymer’ chloride counterpart. Recrystallization of 1:1 silver(I) iodide:tris(2,4,6-trimethoxyphenyl)phosphine (‘tmpp’) mixtures from py and quinoline (‘quin’)/acetonitrile solutions has yielded crystalline materials which have also been characterized by X-ray studies. In both cases the products are salts, the cation in each being the linearly coordinated silver(I) species [Ag(tmpp)2]+, while the anions are, respectively, the discrete [Ag5I7(py)2]2- species, based on the already known but unsolvated [Cu5I 7]2- discrete, and the [Ag5I7] (?|?)2- polymeric, arrays, and polymeric [Ag5I6(quin)](?|?)-. The detailed stereochemistry of the [Ag(tmpp)2]+ cation is a remarkably constant feature of all structures, as is its tendency to close-pack in sheets normal to their P-Ag-P axes. The far-IR spectra of the above species and of several related complexes have been recorded and assigned. The vibrational modes of the single stranded polymeric AgX chains in [XAg(pip) 2](?|?) (X = Cl, SCN) are discussed, and the assignments nu(AgX) = 155, 190 cm-1 (X = Cl) and 208 cm -1 (X = SCN) are made. The nu(AgX) and nu(AgN) modes in the cubane tetramers [XAg(pip)]4 (X = Br, I) are assigned and discussed in relation to the assignments for the polymeric AgX:pip (1:2) complexes, and those for the polymeric [XAg(quin)](?|?) (X = Cl, Br) compounds. The far-IR spectra of [Ag(tmpp)2]2[Ag 5I7(py)2] and its corresponding 2-methylpyridine complex show a single strong band at about 420 cm-1 which is assigned to the coordinated tmpp ligand in [Ag(tmpp)2] +, and a partially resolved triplet at about 90, 110 and 140 cm -1 which is assigned to the nu(AgI) modes of the [Ag 5I7L2]2- anion. An analysis of this pattern is given using a model which has been used previously to account for unexpectedly simple nu(CuI) spectra for oligomeric iodocuprate(I) species.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

What I Wish Everyone Knew About Bis(acetylacetone)copper

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Treatment of [M(H2Li)] with U(acac)4 in refluxing pyridine led to the formation of the trinuclear complexes [{MLi(py)x}2U] [L1 = N,N?-bis(3-hydroxysalicylidene)-2,2-dimethyl-1,3-propanediamine and M = Ni, Cu or Zn; L2 = N,N?-bis(3-hydroxysalicylidene)-1,3-propanediamine and M = Cu or Zn; L3 = N,N?-bis(3-hydroxysalicylidene)-2-methyl-1,2-propanediamine and M = Ni, Cu or Zn; x = 0 or 1]. The dinuclear compounds [ML3(py)U(acac)2] (M = Cu, Zn) were isolated from the reaction of [M(H2L3)] and U(acac)4 in pyridine at 60C. The crystal structures of the trinuclear complexes are built up by two orthogonal MLi(py)x units which are linked to the central uranium ion by the two pairs of oxygen atoms of the Schiff base ligand; the U(IV) ion is found in the same dodecahedral configuration but the Cu(II) ion coordination geometry and the Cu … U distance are different by passing from L1 or L2 to L3, due to the shortening of the diimino chain of L3. These geometrical parameters seem to have a great influence on the magnetic behaviour of the complexes since the Cu-U coupling in [{CuLi(py)x}2U] (i = 1, 2) is ferromagnetic while it is antiferromagnetic in [{CuL3(py)x}2U]. In the compounds [{CuL3(py)x}2U] and [CuL3(py)U(acac)2], the Cu coordination and the Cu … U distance are very similar, and both exhibit an antiferromagnetic interaction.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

The Shocking Revelation of Bis(acetylacetone)copper

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There were studied polyamide composites containing copper(II) oxide (CuO) and copper(II) acetoacetate Cu(acac)2, which after laser irradiation became fully prepared for an electroless metallization process. The composites were produced by use of typical processing methods such as extrusion and injection moulding. They were then irradiated with various numbers of ArF excimer laser pulses (lambda = 193 nm) at different fluences. The metallization procedure of the laser-irradiated samples was performed by use of a commercial metallization bath and formaldehyde as a reducing agent. The samples were examined using the FTIR and XPS techniques. Examinations were focused on elucidation of possible chemical reactions between CuO and Cu(acac)2, affected by both thermal processing and laser irradiation. It was found that CuO was efficiently reduced to Cu(0) and that surface became highly active for the direct electroless metallization. A chemical reaction model for this reduction is proposed as well.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

Interesting scientific research on Cuprous thiocyanate

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Copper(I) complexes are studied for various potential applications due to their luminescence properties. However, issues have been identified regarding the stability of heteroleptic compounds. As a novel strategy, we propose to modify existing copper(I) complexes by introduction of molecular bridges between the different ligands. We report the synthesis and chemical properties of the complexes of 8-(diphenylphosphanyl-oxy)quinoline (POQ), a combination of a phosphine and a N-heterocycle with CuX (X = Cl, Br, I and SCN). The photophysical properties of the materials were studied. However, all four compounds were found to be labile in solution upon contact with trace amounts of water. Two POQ complexes and the decomposition products were identified as tetraphenyldiphosphoxane complexes with single crystal X-ray diffraction. We propose a design rule to prevent this behavior in future development steps.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

Decrypt The Mystery Of Cuprous thiocyanate

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The hydro/solvothermal reactions of Cu(I)/Cu(II) salt, NaN3, and acetonitrile in water or methanol yield two noninterpenetrated supramolecular networks containing 1D hexagonal and square nanochannels, {[Cu(Mtta)]·0.17H2O}n (1) and its pseudopolymorph [Cu(Mtta)]n (2) (Mtta = 5-methyl tetrazolate), involving ligand insitu formation by cycloaddition of nitriles and azides. The copper-(I) centers in both complexes are all bridged by Mtta ligands, forming the different shapes of the cavity. 1 exhibits an unprecedented uniform (8, 3) topological metal network, whereas 2 is a 3-connected (8210) metal net.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Thiazolidinone derivatives of formula (I): STR1 in which R1, R2, R3, R4 and R5 are various atoms or organic groups, Ar is an aromatic group and n is an integer have valuable pharmacological activities including the ability to reduce blood glucose levels and blood lipid levels.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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The flexible, multi dentate, heteroelemental, dipodal ligands; bis(2pyridylthio)methane, (PyS)2CH2 (Py = pyridyl = C5H4N), (PymS)2CH2, bis(2pyrimidylthio)methane, and bipyrimidyldisulfide, (PymS)2 (Pym = pyrimidine, C4H3N2), were reacted with a series of copper precursors to determine whether monomeric compounds, cubane clusters or polymeric chains would be obtained. Copper(II) chloride, copper(I) cyanide and copper(I) thiocyanate afforded infinite polymeric chains while copper(I) iodide afforded tetranuclear clusters supported by two ligand molecules. All products were characterized in the solid-state by X-ray crystallography.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Compositions containing and methods employing, as the essential ingredient, novel disubstituted xanthone carboxylic acid compounds which are useful in the treatment of allergic conditions. Methods for preparing these compounds and compositions and intermediates therein are also disclosed. 5-Methylsulfinyl-7-isopropoxyxanthone-2-carboxylic acid and 5,7-di(methylsulfinyl)xanthone-2-carboxylic acid are illustrated as representative compounds.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”