CuI‐Catalyzed Alkyne–Azide “Click” Cycloadditions from a Mechanistic and Synthetic Perspective

Light-Emitting Self-Assembled Materials Based on d(8) and d(10) Transition Metal Complexes.

The coordination chemistry of pyrazole-derived ligands

This contribution presents an overview of the principal classes of second-order nonlinear optical (NLO) transition metal (organometallic and coordination) complexes and illustrates how organometallic and coordination chemistry can offer a very large variety of NLO structures in relation to the metal nd configuration, oxidation state, spin state, etc. Moreover, metal complexes can satisfy the very different demands of second-order NLO materials such as switchable, tuneable, and multidimensional NLO properties, depending on the subtle interplay of structure–property relationships. Recent advances and perspectives in metal complexes as NLO materials are also presented.

Second-order nonlinear optical properties of transition metal complexes

Mechanism of the Ligand-Free CuI-Catalyzed Azide–Alkyne Cycloaddition Reaction†

Phosphine Substitution in Indenyl- and Cyclopentadienylruthenium Complexes. Effect of the η5 Ligand in a Dissociative Pathway

Novel binuclear copper(I) complexes of the types [Cu2(µ-dppm)2(MeCN)n]X2(n= 2 or 4) and [Cu2(µ-dppm)3]X2(X = BF4 or ClO4, dppm = Ph2PCH2PPh2) have been prepared. Proton and 31P-{1H} n.m.r. studies at room temperature show that they undergo ligand-dissociation processes in solution. The crystal structure of [Cu2(µ-dppm)2(MeCN)4][ClO4]2 has been determined by X-ray methods. Crystals are monoclinic, space group C2/c with Z= 4 in a unit cell of dimensions a= 22.407(9), b= 13.052(6), c= 21.522(8)A, and β= 108.69(3)°. The structure has been solved from diffractometer data by Patterson and Fourier methods and refined by full-matrix least squares to R= 0.079 for 3 907 observed reflections [I > 3σ(I)]. The structure consists of [Cu2(µ-dppm)2(MeCN)4]2+ cations and of disordered perchlorate anions. In the cations the two copper atoms are bridged by dppm ligands to give eight-membered Cu2P4C2 rings. The tetrahedral co-ordination around the copper is completed by two nitrogen atoms from acetonitrile ligands.

Binuclear copper(I) complexes containing bis(diphenylphosphino)methane bridging ligands: crystal structure of [Cu2(µ-dppm)2(MeCN)4][ClO4]2

[Cu3(.mu.3-.eta.1-C.tplbond.CPh)2(.mu.-Ph2PCH2PPh2)3][BF4], a triangulo copper(I) complex with an unprecedented bicapping system of two asymmetric .mu.3-.eta.1-acetylide ligands

Large second-order nonlinear optical properties of novel organometallic (sigma-aryl-enynyl)ruthenium complexes

Synthesis and characterization of triangulo copper(I) complexes containing mono- and bicapping systems of asymmetric .mu.3-.eta.1-acetylide ligands: molecular structures of [Cu3(.mu.3-.eta.1-C.tplbond.CPh)(.mu.-dppm)3][BF4]2, [Cu3(.mu.3-.eta.1-C.tplbond.CPh)2(.mu.-dppm)3][BF4], and [Cu3(.mu.3-.eta.1-C.tplbond.CPh)(.mu.3-Cl)(.mu.-dppm)3][BF4] [dppm = bis(diphenylphosphino)methane]

José Gimeno

Papers

Phosphine Substitution in Indenyl- and Cyclopentadienylruthenium Complexes. Effect of the η5 Ligand in a Dissociative Pathway

Binuclear copper(I) complexes containing bis(diphenylphosphino)methane bridging ligands: crystal structure of [Cu2(µ-dppm)2(MeCN)4][ClO4]2

[Cu3(.mu.3-.eta.1-C.tplbond.CPh)2(.mu.-Ph2PCH2PPh2)3][BF4], a triangulo copper(I) complex with an unprecedented bicapping system of two asymmetric .mu.3-.eta.1-acetylide ligands

Large second-order nonlinear optical properties of novel organometallic (sigma-aryl-enynyl)ruthenium complexes