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

IR and Raman Spectroscopy of Inorganic, Coordination and Organometallic Compounds*

Unsymmetrical 3- and 5-substituted bis(pyrazolyl)borate system

A comprehensive survey of the syntheses and of spectroscopic, analytical and structural data of silver(I), copper(I), and copper(II) complexes containing scorpionate and related ligands and prepared by this group has been reported. This review outlines the possible strategies that can be used in this field for the synthesis of analogous complexes. Statistical analyses of structural features are reported as a function of (1) the steric and electronic properties of the scorpionate ligand, (2) the steric and electronic properties of eventual ancillary ligands, and (3) the nature of the counter-ion. The most important results obtained in this field have been also summarized.

Copper and Silver Derivatives of Scorpionates and Related Ligands

Viscoelastic investigation by ultrasonic shear waves of liquid eutectic mixture methylurea-ammonium sulfamate

New silver(I) derivatives containing triorganophosphines and the anionic dihydrobis(1-imidazolyl)borate [H2B(im)2]−, or the tetrakis(1-imidazolyl)borate ligand, [B(im)4]−, have been synthesized from reaction of AgNO3 with PR3 (R = phenyl, cyclohexyl, o-, m- or p-tolyl) or (PPh2R′) (R′ = methyl or ethyl) and K{H2B(im)2}·DMAC [DMAC = dimethylacetamide) or K[B(im)4]. Binuclear [Ag(PR3)2{(im)BX2(im)}]2 or polymeric [Ag(PR3){(im)BX2(im)}]n (X = H or imidazolate) complexes have been obtained and fully characterized by elemental analyses and FT-IR in the solid state and by NMR (1H and 31P) spectroscopy and conductivity measurements in solution. Solution data are consistent with partial dissociation of complexes, occurring through breaking of both Ag–N and Ag–P bonds. The structures of [Ag{P(C6H4Me-p)3}2{(im)BH2(im)}]2·2CHCl3, [Ag{P(cy)3}{(im)BH2(im)}]n and [{P(cy)3}Ag{(im)B(im)2(im)}]2·MeCN have been determined by single crystal X-ray studies. The [Ag{P(cy)3}{(im)BH2(im)}]n adduct is a single-stranded polymer containing three-coordinate silver atoms (PAgN2 core), while in the two other adducts, the silver atoms are four-coordinate (P2AgN2 cores). In all structures the two silver atoms are bridged by independent imidazolate donors from a pair of (im)BX2(im) moieties.

Bridged poly(1-imidazolyl)borate silver(I) complexes containing tertiary mono(phosphine) ligands. The first structurally authenticated bis(imidazolyl)borate metal complex

Carlo Santini

Papers

IR and Raman Spectroscopy of Inorganic, Coordination and Organometallic Compounds*

Unsymmetrical 3- and 5-substituted bis(pyrazolyl)borate system

Copper and Silver Derivatives of Scorpionates and Related Ligands

Viscoelastic investigation by ultrasonic shear waves of liquid eutectic mixture methylurea-ammonium sulfamate

Bridged poly(1-imidazolyl)borate silver(I) complexes containing tertiary mono(phosphine) ligands. The first structurally authenticated bis(imidazolyl)borate metal complex