Four Cu(I) complexes were synthesized with a family of pyridylmethylamide ligands, HLR [HLR = N-(2-pyridylmethyl)acetamide, R = null; 2,2-dimethyl-N-(2-pyridylmethyl)propionamide, R = Me3; 2,2,2-triphenyl-N-(2-pyridylmethyl)acetamide, R = Ph3)]. Complexes 1–3 were synthesized from the respective ligand and [Cu(CH3CN)4]PF6 in a 2 : 1 molar ratio: [Cu(HL)2]PF6 (1), [Cu2(HLMe3)4](PF6)2 (2), [Cu(HLPh3)2]PF6 (3). Complex 4, [Cu(HL)(CH3CN)(PPh3)]PF6, was synthesized from the reaction of HL with [Cu(CH3CN)4]PF6 and PPh3 in a 1 : 1 : 1 molar ratio. X-Ray crystal structures reveal that complexes 1, 3 and 4 are mononuclear Cu(I) species, while complex 2 is a Cu(I) dimer. The copper ions are four-coordinate with geometries ranging from distorted tetrahedral to seesaw in 1, 2, and 4. Complexes 1 and 2 are very air sensitive and they display similar electrochemical properties. The coordination geometry of complex 3 is nearly linear, two-coordinate. Complex 3 is exceptionally stable with respect to oxidation in the air, and its cyclic voltammetry shows no oxidation wave in the range of 0–1.5 V. The unusual inertness of complex 3 towards oxidation is attributed to the protection from bulky triphenyl substituent of the HLPh3 ligand. A new geometric parameter for four-coordinate compounds, τ4, is proposed as an improved, simple metric for quantitatively evaluating the geometry of four-coordinate complexes and compounds.

Structural variation in copper(I) complexes with pyridylmethylamide ligands: structural analysis with a new four-coordinate geometry index, tau4.

Advances in copper complexes as anticancer agents.

Mechanisms of the H2-hydrogenation and transfer hydrogenation of polar bonds catalyzed by ruthenium hydride complexes

http://www.sciencemadness.org/talk/files.php?pid=302583&aid=26587

Azole-based energetic salts.

2.3.5. Multi-NHCs Linked by Spacers 3568 2.4. The Ag2O Route 3570 2.4.1. Feasibility 3570 2.4.2. Complications 3571 2.4.3. Theoretical Consideration 3572 2.5. Applications 3572 2.5.1. Ag(I)-NHCs in NHC Transfer 3572 2.5.2. Ag(I)-NHCs in Catalysis 3572 2.5.3. Ag(I)-NHCs in Medicine 3572 2.5.4. Ag(I)-NHCs in Nanomaterials 3573 3. Au(I)and Au(III)-NHCs 3573 3.1. Historical Background 3573 3.2. General Synthetic Methods 3573 3.3. Formation of Au(I)and Au(III)-NHCs 3574 3.3.1. Neutral [Au(NHC)L] 3574 3.3.2. Ionic [Au(NHC)L][Anion] 3576 3.3.3. Multinuclear Au(I)-NHCs 3578 3.3.4. Other Classes of Au(I)-NHCs 3578 3.3.5. Au(III)-NHC Complexes 3579 3.4. Applications 3579 3.4.1. Au(I)and Au(III)-NHCs in Catalysis 3579 3.4.2. Au(I)-NHCs in Medicine 3580 4. Cu(I)and Cu(II)-NHCs 3581 4.1. Historical Background 3581 4.2. General Synthetic Methods 3582 4.3. Formation of Cu(I)and Cu(II)-NHCs 3583 4.3.1. Complexes Containing the Cu(NHC)2 Core 3583 4.3.2. [Cu(NHC)(Halide)] 3583 4.3.3. [Cu(NHC)(Ligand)] 3584 4.3.4. Multinuclear Cu(I)and Cu(II)-NHCs 3589 4.4. Catalysis 3591 4.4.1. Past Events 3591 4.4.2. Recent Advancements 3591 5. Photoluminescence 3592 6. Conclusions 3594 7. Abbreviations 3594 8. Acknowledgments 3595 9. References 3595

Coinage Metal−N-Heterocyclic Carbene Complexes

Synthesis, characterization and preliminary biological evaluation of [Cu-64] ethhylenedicysteine-nitroimidazole and comparative studies with [F-18] fluoromisonidazole

Bis(pyrazol-1-yl)acetic acid (HC(pz)2COOH) and bis(3,5-dimethyl-pyrazol-1-yl)acetic acid (HC(pzMe2)2COOH) were converted into the methyl ester derivatives 1 (LOMe) and 2 (L2OMe), respectively, and were used for the preparation of silver(I) complexes 3–5. The Ag(I) complexes were prepared by the reaction of AgNO3 and 1,3,5-triaza-7-phosphaadamantane (PTA) or triphenylphosphine (PPh3) with LOMe and L2OMe in methanol solution. All Ag(I) complexes showed a significant in vitro antitumor activity, proving to be more effective than the reference drug cisplatin in the in-house human cancer cell line panel containing examples of different solid tumors. Compounds were particularly effective against the highly aggressive and intrinsically resistant human small-cell lung carcinoma (SCLC) cells, either in 2D and 3D cancer cell models. Mechanistic studies revealed their ability to accumulate into cancer cells and to selectively target Thioredoxin (TrxR), thus leading to redox homeostasis unbalance and ultimately inducing cancer cell death through apoptosis.

/pdf/novel-silver-complexes-based-on-phosphanes-and-ester-1k1y67cc.pdf

Novel Silver Complexes Based on Phosphanes and Ester Derivatives of Bis(pyrazol-1-yl)acetate Ligands Targeting TrxR: New Promising Chemotherapeutic Tools Relevant to SCLC Management

Copper(Ii) Complexes Based on Isopropyl Ester Derivatives of Bis(Pyrazol-1-Yl)Acetate Ligands with Catalytic Potency in Organic Macro(Molecules) Synthesis

Surface organometallic chemistry: reaction of tris(allyl)rhodium with surfaces of silica, alumina, titania, and magnesia. [Erratum to document cited in CA116(23):235831z]

New silver(I) derivatives containing triorganophosphines and anionic dihydrobis(pyrazol-1-yl)borates have been prepared from AgNO3 and PR3 (R = phenyl, benzyl, cyclohexyl, o-, m- or p-tolyl) or PPh2R′ (R′ = methyl or ethyl) and K[H2B(pz)2] or K[H2B(3,5-Me2pz)2] (Hpz = pyrazole); their solid state and solution properties have been investigated through analytical and spectroscopic measurements (IR, 1H and 31P NMR). The compounds are stable, soluble in chlorinated solvents and non-electrolytes in CH2Cl2 and acetone solutions. The structures of [Ag{H2B(pz)2}(PPh3)2], [Ag{H2B(3,5-Me2pz)2}(PEtPh2)], and [Ag{H2B(3,5-Me2pz)2}(PCy3)] have been determined by X-ray crystallographic studies. In these compounds the dihydrobis(pyrazol-1-yl)borate ligand is bidentate, with the silver(I) centre adopting a tetrahedral (first) or trigonal geometry (last two).

Carlo Santini

Papers

Synthesis, characterization and preliminary biological evaluation of [Cu-64] ethhylenedicysteine-nitroimidazole and comparative studies with [F-18] fluoromisonidazole

Novel Silver Complexes Based on Phosphanes and Ester Derivatives of Bis(pyrazol-1-yl)acetate Ligands Targeting TrxR: New Promising Chemotherapeutic Tools Relevant to SCLC Management

Copper(Ii) Complexes Based on Isopropyl Ester Derivatives of Bis(Pyrazol-1-Yl)Acetate Ligands with Catalytic Potency in Organic Macro(Molecules) Synthesis

Surface organometallic chemistry: reaction of tris(allyl)rhodium with surfaces of silica, alumina, titania, and magnesia. [Erratum to document cited in CA116(23):235831z]

Solution and solid-state structural properties of silver(I) dihydrobis(pyrazolyl)borate compounds with tertiary mono(phosphine) ligands