- Crystal structure of copper(I) thiosemicarbazone complex [CuI(PPh3)(catsc)]
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In this paper, we report the preparation of a four-coordinated copper(I) thiosemicarbazone complex [CuI(PPh3)(catsc)] from the reaction of PPh3 and catsc (3-phenylpropenalthiosemicarbazone) with CuI. The synthesized complex is characterized by elemental analyses (CHNS) and FT-IR spectroscopy. The crystal structure of [CuI(PPh3)(catsc)] is investigated by single crystal X-ray diffraction. The catsc coordinates to the copper(I) ion as a bidentate ligand via the N and S atoms. The complex has a distorted tetrahedral coordination geometry.
- Shahsavani,Feizi,Eigner,Dusek,Khalaji
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- Toward multifunctional "clickable" diamond nanoparticles
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Nanodiamonds (NDs) are among the most promising new carbon based materials for biomedical applications, and the simultaneous integration of various functions onto NDs is an urgent necessity. A multifunctional nanodiamond based formulation is proposed here. Our strategy relies on orthogonal surface modification using different dopamine anchors. NDs simultaneously functionalized with triethylene glycol (EG) and azide (N3) functions were fabricated through a stoichiometrically controlled integration of the dopamine ligands onto the surface of hydroxylated NDs. The presence of EG functionalities rendered NDs soluble in water and biological media, while the N3 group allowed postsynthetic modification of the NDs using "click" chemistry. As a proof of principle, alkynyl terminated di(amido amine) ligands were linked to these ND particles.
- Khanal, Manakamana,Turcheniuk, Volodymyr,Barras, Alexandre,Rosay, Elodie,Bande, Omprakash,Siriwardena, Aloysius,Zaitsev, Vladimir,Pan, Guo-Hui,Boukherroub, Rabah,Szunerits, Sabine
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- Steric demands in the formation of heteroleptic Cu(I) complexes with α-diimines and triphenylphosphine
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The synthesis and the study of the molecular structure of a series of heteroleptic copper(I) compounds with triphenylphosphine and α-diimines presenting a varying degree of bulk at their chelating cite is reported. The most sterically crowded diimine acts as a monodentate ligand towards copper(I) promoting bridging of the halogen atom present in the metal coordination sphere and formation of a dimer. Evidence for this behavior is obtained from the electronic spectra and semiempirical quantum chemical calculations with MOPAC. Steric demands in all the studied compounds preclude coordination of silver(I) under similar reaction conditions.
- Tseriotou, Eleni,Tzimopoulos, Dimitris,Hatzidimitriou, Antonis,Akrivos, Pericles
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p. 152 - 157
(2018/07/29)
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- Synthesis, structure and cytotoxicity evaluation of complexes of N1-substituted-isatin-3-thiosemicarbazone with copper(I) halides
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Synthesis of Isatin-N1-methyl-thiosemicarbazone (H2itsc-N1-Me, H2L1) and isatin-N1-ethyl-thiosemicarbazone (H2itsc-N1-Et, H2L2) has been carried out and the effect of substituents (at N1 atom of isatin-3-thiosemicarbazones) on nuclearity of copper(I) halide complexes has been investigated. Reactions of copper(I) halides (X = I, Br, Cl) with H2L1 and H2L2 using Ph3P as co-ligand in 1:1:1 (M:L:PPh3) molar ratio in acetonitrile yielded complexes of stoichiometry [CuX(H2L1)(Ph3P)] (X = I, C1; Br, C2; Cl, C3) and [CuX(H2L2)(Ph3P)] (X = I, C4; Br, C5; Cl, C6) respectively. All these complexes have been characterized using analytical and spectroscopic data (IR, 1H NMR and ESI mass). The single crystal structure has been solved for H2L1 and C2. The complex C2 has distorted tetrahedral geometry around copper(I) and isatin-N1-methyl-thiosemicarbazone coordinated to metal center as neutral, bidentate, N3, S-chelating ligand. Elemental analysis suggested the presence of one acetonitrile molecule in complexes C3 and C6 and half CH3CN in complexes C2 and C4 as solvent of crystallization. MTT assay, supported by docking studies have revealed the cytotoxic nature of the compounds C1-C6.
- Khan, Ashiq,Jasinski, Jerry P.,Smoleaski, Victoria A.,Paul, Kamaldeep,Singh, Gurpinder,Sharma, Rekha
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supporting information
p. 119 - 126
(2016/06/01)
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- Copper(I)-catalyzed stereoselective synthesis of (1E,3E)-2- sulfonyl-1,3-dienes from N-propargylic sulfonohydrazones
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A new method for the stereoselective synthesis of highly substituted (1E,3E)-2-sulfonyl-1,3-dienes from N-propargylic sulfonohydrazone derivatives has been developed via copper(I)-catalyzed [3,3] rearrangement and highly regioselective migration of the sulfonyl group. Copyright
- Zhu, Yu,Tang, Hai-Tao,Zhan, Zhuang-Ping
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supporting information
p. 1291 - 1296
(2013/06/26)
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- Novel phosphinite and phosphonite copper(I) complexes: Efficient catalysts for click azide-alkyne cycloaddition reactions
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The preparation of novel phosphinite- and phosphonite-bearing copper(I) complexes of the general formula [CuX(L)] is reported. These compounds, which remain scarce in the literature, could be prepared using readily available starting materials and were spectroscopically and structurally characterized. These complexes, together with their known phosphine and phosphite analogues, were then applied to the 1,3-dipolar cycloaddition of azides and alkynes, to find that the new complexes displayed the best activities. Full optimization of the reaction conditions resulted in a noteworthy Click catalytic system, active under very mild reaction conditions in the absence of any additive and using low metal loadings.
- Lal, Steven,McNally, Jayne,White, Andrew J. P.,Diez-Gonzalez, Silvia
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p. 6225 - 6232
(2012/01/12)
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- The influence of substituents (R) at N1 atom of thiophene-2-carbaldehyde thiosemicarbazones {(C4H3S)HC2{double bond, long}N3-N(H)-C1({double bond, long}S)N1HR} on bonding, nuclea
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The nuclearity, bonding and H-bonded networks of copper(I) halide complexes with thiophene-2-carbaldehyde thiosemicarbazones {(C4H3S)HC2{double bond, long}N3-N(H)-C1({double bond, long}S)N1
- Lobana, Tarlok Singh,Sharma, Rekha,Castineiras, Alfonso,Hundal, Geeta,Butcher, Ray Jay
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p. 3547 - 3554
(2009/10/30)
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- Quantitative evaluation of the factors contributing to the copper effect in the stille reaction
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The relative importance of the factors contributing to the accelerating effect of CuI on [PdL4]-catalyzed couplings of R1I and R2SnBu3 (copper effect) has been quantitatively evaluated in THF for R1 = 3,5-C6Cl2F3; R2 = vinyl, C6H4-4-OMe; L = AsPh3, PPh3, using spectroscopic and kinetic methods. The 19F NMR kinetic data show that the rate enhancement produced by addition of CuI is strongly related with the autoretardation effect intrinsic to [PdL4] catalysts and is almost independent of the organotin reagent (vinyl, aryl). The autoretardation is due to the release of 2 equiv of L during the oxidation of [PdL4] to yield trans-[PdR1IL2], which is the species undergoing transmetalation. CuI does not promote the dissociation of L from trans-[PdR1IL2], but it captures part of the free neutral ligand L and therefore mitigates the autoretardation produced by the presence of free L on the rate-determining associative transmetalation. In the conditions studied (Pd:Cu = 1:2; T = 322.6 K; THF as solvent), for L = AsPh3 the CuI added captures about 25% of the free AsPh3 and the copper effect compensates only ca. 1% of the autoretardation, whereas for L = PPh3 the CuI captures about 99% of the free PPh3 and the compensation is about 30%. This remarkable variation is caused by the combined effect of two independent factors: (i) The catalyst [Pd(PPh3)4] is more autoretarded than [Pd(AsPh3)4]; and (ii) CuI is a more effective scavenger for PPh3 than for AsPh3.
- Casado, Arturo L.,Espinet, Pablo
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p. 1305 - 1309
(2008/10/08)
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- Preparation and properties of trans-Pd(Ar) (C≡CPh) (PEt3)2. Intermolecular alkynyl ligand transfer between copper(I) and palladium(II) complexes relevant to palladium complex catalyzed cross-coupling of terminal alkyne with haloarene in the presence of CuI cocatalyst
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trans-Pd(C6H4Me-p)(I)(PEt3)2 (2a) reacts with [Cu(C≡CPh)(PPh3)]4 (Pd:Cu = 1:1) at room temperature to give the cross-coupling product PhC≡CC6H4Me-P (3a) in 74% yield. Reactions of 2a with [Cu(C≡CPh)(PPh3)I4 at -30 °C as well as of trans-Pd(C6H4X-P)(I)(PEt3)2 (2a, X = Me; 2b, X = OMe; 2c, X = F) with the alkynylcopper complex and additional PPh3 (2 mol/ mol of Cu) at room temperature give mixtures of PhC≡CC6H4X-P (3a, X = Me; 3b, X = OMe; 3c, X = F) and trans-Pd(C6H4X-P)(C≡CPh)(PEt3) 2 (4a, X = Me; 4b, X = OMe; 4c, X = F). Complexes 4a,b have been isolated from the latter reaction mixtures and fully characterized. Pd-C(alkynyl) and Pd-C(aryl) bond distances in 4a are 2.016(8) and 2.062(7) A, respectively. Addition of Cul to a solution of 4a at room temperature causes complete conversion of 4a into 2a and 3a in 1 h. The relative molar ratio between 2a and 4a after reaction for 2 h varies, depending on the amount of added PPh3. Reactions of trans-Pt(C6H4X-p)(I)(PEt3)2 (5b, X = OMe; 5c, X = F) with [Cu(C≡CPh)(PPh3)]4 at room temperature afford trans-Pt(C6H4X-p)(C≡CPh)(PEt3) 2 (6b, X = OMe; 6c, X = F), respectively. Heating an equimolar mixture of 4a and 5b at 35-50 °C leads to inter-metal exchange of the alkynyl and iodo ligands, giving 2a and 6b quantitatively. The reaction follows the kinetics that is first order in concentration of 4a and in that of 5b. The kinetic parameters are obtained as ΔH? = 110 kJ mol-1, ΔS? = -58 J mol-1 deg-1, and ΔG? = 127 kJ mol-1 at 298 K. The alkynyl ligand migration from Pd(II) to Pt(II) is enhanced by addition of a catalytic amount of CuI.
- Osakada, Kohtaro,Sakata, Reiko,Yamamoto, Takakazu
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p. 5354 - 5364
(2008/10/08)
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- Synthesis of triangular mixed-metal clusters by the addition of copper electrophiles to an electron-rich rhodium-rhodium bond. X-ray crystal structures of [Rh2(η-C5H5) 2(μ-CO)(μ-Ph2PCH2PPh 2)(μ-CuI)] and [Rh2(η-C5H5) ...
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Full title: Synthesis of triangular mixed-metal clusters by the addition of copper electrophiles to an electron-rich rhodium-rhodium bond. X-ray crystal structures of [Rh2(η-C5H5) 2(μ-CO)(μ-Ph2PCH2PPh 2)(μ-CuI)] and [Rh2(η-C5H5) 2(μ-CO)(μ-Ph2PCH2PPh 2)(μ-AgO2CCH3)]. The new Rh2Cu mixed-metal clusters [Rh2(η-C5H5) 2(μ-CO)(μ-dppm)(μ-CuX)] (X = Cl, 2; X = I, 3; dppm = bis(diphenylphosphino)methane) have been prepared by reacting [Rh2(η-C5H5) 2(μ-CO)(μ-dppm)] (1) with CuX and have been spectroscopically characterized. The structure of 3 has also been established by X-ray crystallography. The compound crystallizes in the orthorhombic space group Pnma with a = 14.002 (2) A?, b = 18.306 (2) A?, c = 13.025 (1) A?, V = 3338.5 A?3, and Z = 4. The structure has been refined to R = 0.034 and Rw = 0.039 for the 1064 reflections with I ≥ 3σ(I). Complex 3 reacts with AgO2CCF3 to yield [Rh2(η-C5H5) 2(μ-CO)(μ-dppm)(μ-AgO2CCF3)] (4) which has been structurally characterized. Crystals of 4 are also orthorhombic of space group Pnma with a = 15.133 (2) A?, b = 18.176 (3) A?, c = 12.656 (1) A?, V = 3481.0 A?3, and Z = 4. R = 0.034 and Rw = 0.034 for the 1993 reflections with I ≥ 3σ(I). In both complexes structurally characterized the three metal atoms define a triangular cluster [in 3 Rh(1)-Rh(1′) = 2.746 (1), Rh(1)-Cu = 2.588 (2) A?; in 4 Rh(1)-Rh(1′) = 2.776 (1), Rh(1)-Ag = 2.719 (1) A?] with the Rh-Rh bond bridged by the dppm and the CO ligands. The rhodium atoms are each symmetrically capped by one η-cyclopentadienyl ligand, and the interplanar angle between the cyclopentadienyl rings can be related to the bulk of the group 11 metal. In 3 the iodine atom is bonded to copper while in 4 the trifluoroacetate group is chelated to the silver atom. The structural features of 3 and 4 have been compared with those of the other compounds of this class already reported. The results show that the formation of stable Rh2Ag and Rh2Cu triangular clusters by addition of electrophiles containing the group 11 metals to 1 requires the use of silver or copper salts of coordinating anions.
- Bruno, Giuseppe,Lo Schiavo, Sandra,Rotondo, Enrico,Piraino, Pasquale,Faraone, Felice
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p. 2502 - 2507
(2008/10/08)
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