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Synthesis, characterization, crystal structures and photophysical properties of copper(I) complexes containing 1,1?-bis(diphenylphosphino) ferrocene (B-dppf) in doubly-bridged mode

Five copper(I) complexes having general formula [Cu2(mu-X) 2(kappa2-P,P-B-dppf)2] (X = Cl(1), Br(2), I(3), CN(4), and SCN(5)) were prepared starting with CuX and B-dppf in 1:1 molar ratio in DCM-MeOH (50:50 V/V) at room temperature. The complexes have been characterized by elemental analyses, IR, 1H NMR, 31P NMR and electronic spectral studies. Molecular structures for 1, 2 and 4 were determined crystallographically. Complexes 1, 2 and 4 exist as centrosymmetric dimers in which the two copper atoms are bonded to two bridging B-dppf ligands and two bridging (pseudo-)halide groups in a mu-eta1 bonding mode to generate nearly planar Cu2(mu-eta1-X)2 framework. Both bridging B-dppf ligands are arranged in antiperiplanar staggered conformation in 1 and 2 (mean value 56.40-56.76), and twisted from the eclipsed conformation (mean value 78.19) in 4. The Phi angle value in 4 is relatively larger as compared to 1 and 2. This seems to indicate that the molecular core [Cu2(mu-eta1-X)2] in 4 is a sterically demanding system that forces the B-dppf ligand to adopt a relatively strained conformation in comparison to less strained system in 1 and 2. All the complexes exhibit moderately strong luminescence properties in the solution state at ambient temperature.

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

 

Brief introduction of Cuprous thiocyanate

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Structural features of di(1-adamantyl)benzylphosphane complexes of Cu(I) and Ag(I)

The sterically bulky di(1-adamantyl)benzylphosphane (L) reacts with the copper(I) compounds, CuX (X = Cl, Br, I and SCN), in a 1:1 ratio to give the salts CuXL. Single crystal X-ray structures for X = Cl, Br and SCN, show that the complexes exist as dimeric species of the type [Cu2X2L2] with the X groups bridging to give each copper a distorted trigonal-planar coordination geometry with a ?PX2? donor site. When [Cu(CH3CN)4]BF4reacts with L in a 1:2 ratio, the two-coordinated complex [CuL2]BF4was formed which has a P?Cu?P angle of 169.46(6), reflecting the influence of the adamantyl groups. The silver(I) 1:2 compound, [AgClL2], has a ?ClP2? donor set with a distorted P?Ag?P bond angle of about 149.02(5). The reduced coordination numbers, irregular structures and distortions of selected angles are a result of the steric bulk (large cone angle) of L. Some of these structural features may also assist in understanding why Pd(0) complexes of L are effective catalysts for the Sonogashira coupling reactions of arylchlorides and alkynes.

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

 

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A mild copper-catalyzed aerobic oxidative thiocyanation of arylboronic acids with TMSNCS

A facile and efficient transformation of arylboronic acids to their corresponding aryl thiocyanates has been successfully developed. Based on the CuCl-catalyzed oxidative cross-coupling reaction between arylboronic acids and trimethylsilylisothiocyanate (TMSNCS) under oxygen atmosphere, the transformation can be readily conducted at ambient temperature. The newly-developed protocol provided a competitive synthetic approach to aryl thiocyanates that can tolerate a broad range of reactive functional groups and/or strong electron-withdrawing groups.

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

 

Archives for Chemistry Experiments of Cuprous thiocyanate

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One-pot synthesis of (ethoxycarbonyl)difluoromethylthioethers from thiocyanate sodium and ethyl 2-(trimethylsilyl)-2,2-difluoroacetate (TMS-CF2CO2Et)

An efficient one-pot cascade methodology for the synthesis of (ethoxycarbonyl)difluoromethyl thioethers is described. Benzyl, allyl, alkyl halides or diazonium salts as the starting materials together with thiocyanate sodium and TMS-CF2CO2Et in the presence of CsF or NaOAc afford a variety of the fluoroalkylthiolated products in moderate to good yields.

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

 

New explortion of 1111-67-7

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Copper(I) pseudohalide coordination polymers containing macrocyclic methylcycloarsoxane (CH3AsO)n (n = 4, 5) or 1,7-dithia-18-crown-6 bridging units

Treatment of an acetonitrile solution of CuCN with methylcycloarsoxane (CH3AsO)n at 110C affords the coordination polymer ?3[CuCN{cyclo-(CH3AsO)4}] (1), in which infinite CuCN zigzag chains are linked by mu-As1,As 3 cyclotetramers (CH3AsO)4 into an open 3-D framework. Under similar solvothermal conditions, reaction of CuSCN with (CH3AsO)n in the presence of KSCN leads to metal-mediated ring expansion of the cycloarsoxane to yield the complex ? 1[{K[cyclo-(CH3AsO)5]2}Cu(NCS) 2] (2). This contains discrete [Cu(NCS-kappaN)2{cyclo- (CH3AsO)5kappaAs}2]- anions that bridge kappa10O coordinated potassium cations into infinite chains. In contrast, the structure directing role of the [K(1,7DT18C6) 2]+ sandwich building units for the solvothermal product ?3[{K(1,7DT18C6)2}Cu6(CN) 7] (3) (1,7DT18C6 = 1,7-dithia-18-crown-6) leads to formation of an open ?3[{Cu6(CN)7} -] framework. Individual [K(1,7DT18C6)2]+ moieties bridge Cu Atoms in a mu-S1,S7 mode and are encapsulated within the large [Cu26(CN)28]2- cages of the cyanocuprate(I) network.

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

 

Properties and Exciting Facts About Cuprous thiocyanate

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Improving the efficiency and stability of inverted perovskite solar cells by CuSCN-doped PEDOT:PSS

Hole transport layer (HTL) is important in inverted perovskite solar cells (PSCs) to facilitate the hole extraction and suppress the charge recombination for high device performance. Based on the widely used HTL material of poly(ethylenedioxythiophene) (PEDOT):poly(styrenesulfonate) (PSS), we proposed a new HTL modification method using the widely available copper(I) thiocyanate (CuSCN); the doping of CuSCN NH3 [aq] in PEDOT:PSS followed by low-temperature annealing results in reduced energy barrier, improved charge extraction efficiency and increased the mean size of perovskite crystal of the PEDOT:PSS-CuSCN HTL-based inverted PSCs. Significantly improved device performance was observed with open current voltage over 1.0 V and power conversion efficiency (PCE) up to 15.3%, which is 16% higher in PCE than that of the PEDOT:PSS-based PSCs. More impressively, with a lower acidity than PEDOT:PSS, the PEDOT:PSS-CuSCN HTL enables excellent long-term stability of the inverted PSCs, exhibiting almost doubly improved device stability at the same storage condition. Thus, the successful application of CuSCN doping in PEDOT:PSS HTLs should provide a novel approach for the development of high-performance HTLs for highly efficient and stable PSCs.

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

 

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Syntheses, crystal structures and nonlinear optical properties of heteronuclear clusters [MS4Cu4(SCN)2(NC5H5) 6] (M=W, Mo)

The title compounds [MS4Cu4(SCN)2(NC5H5) 6] (M=W (1); M=Mo (2); NC5H5=pyridine) were obtained by the reaction of (NH4)2MS4, CuSCN, KSCN and pyridine. The X-ray analyses of 1 and 2 show that four edges of the tetrahedral MS42- core are coordinated by four copper atoms, giving an MS4Cu4 aggregate of approximate D2h symmetry. The nonlinear optical properties of 1 and 2 were investigated by a Z-scan technique with 7 ns laser pulses of 532 nm. The third-order nonlinearities were determined with alpha2=4.3¡Á10-5 and 4.1¡Á10-5 cm W-1 M-1; and n2=-4.3¡Á10-10 and -4.1¡Á10-10 cm2 W-1 M-1, respectively, for compounds 1 and 2.

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

 

Top Picks: new discover of 1111-67-7

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The structural definition of adducts of stoichiometry MX:dppx (1:1) M = CuI, AgI, X = simple anion, dppx=Ph2P(CH 2)xPPh2, x = 3-6

Single crystal X-ray structural characterizations are recorded for a wide range of adducts of the form MX:dppx (1:1)(n), M = silver(I) (predominantly), copper(I), X = simple (pseudo-) halide or oxy-anion (the latter spanning, where accessible, perchlorate, nitrate, carboxylate – a range of increasing basicity), dppx=bis(diphenylphosphino)alkane, Ph2P(CH 2)xPPh2, x = 3-6. Adducts are defined of two binuclear forms: (i) [LM(mu-X)2L], with each ligand chelating a single metal atom, and (ii) [M(mu-X)2(mu-(P-L-P?)) 2M?] where both ligands L and halides bridge the two metal atoms; a few adducts are defined as polymers, the ligands connecting M(mu-X)2M? kernels, this motif persisting in all forms. Synthetic procedures for all adducts have been reported. All compounds have been characterized both in solution (1H, 13C, 31P NMR, ESI MS) and in the solid state (IR).

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

 

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Tuning chemistry of CuSCN to enhance the performance of TiO 2/N719/CuSCN all-solid-state dye-sensitized solar cell

CuSCN with enhanced p-type conductivity was prepared by replacing some of the cuprous sites by triethylamine coordinated Cu(i) with concomitant (SCN) 2 doping to introduce more holes. A compound Cu5[(C 2H5)3N]3(SCN)11 was isolated and well characterized. A 41% enhancement of energy conversion efficiency of the TiO2/N719/modified CuSCN cell from the best reported value and more than a factor of ten from bare CuSCN was achieved.

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

 

More research is needed about Cuprous thiocyanate

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The coordination chemistry of mono and bis(di-2-pyridylamine)copper(II) complexes: Preparation, characterization and crystal structures of [Cu(L)(NO2)2], [Cu(L)(H2O)2(SO4)], [Cu(L)2(NCS)](SCN)¡¤0.5DMSO and [Cu(L)2(SCN)2]

The crystal structures of two mono(dpyam)copper(II) complexes, [Cu(dpyam)(NO2)2] (1) and [Cu(dpyam)(H2O)2(SO4)] (2) and two dithiocyanate compounds containing bis(dpyam)copper(II) units, [Cu(dpyam)2(NCS)](SCN)¡¤0.5DMSO (3) and [Cu(d- pyam)2(SCN)2] (4) have been determined by X-ray crystallography. The second orthorhombic form of the monomeric Cu(II) complex 1 was obtained by the reaction of di-2-pyridylamine (dpyam) with CuCl and NaNO2 in water-methanol solution. Each copper(II) ion in 1 exhibits a tetrahedrally-distorted square base of the CuN2O2 chromophore, with off-the-z-axis coordinated nitrito groups weakly bound in approximately axial positions. Complex 2 is an example of a polymeric copper(II) derivative containing the bidentate bridging sulfate ligand in the long-bonded axial positions. Each copper(II) ion in 2 shows an elongated tetragonal octahedral stereochemistry. The CuN4N? chromophore of 3 involves a square-based pyramidal structure, slightly distorted towards a trigonal bipyramidal stereochemistry, tau = 0.13. One of the SCN- anions is bonded to the copper(II) ion via the N atom in the axial position of the square pyramid. Complex 4 is centrosymmetric and octahedrally elongated, with the SCN- anions coordinating in axial positions via the S atom. The structures of complexes 1-4 and their ESR and electronic reflectance spectra are compared with those of related complexes.

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