Synthesis and properties of h5-cyclopentadienyl-(triphenylphosphine)silver(I)

The title compound has been prepared by treatment of a solution of cyclopentadienylsodium and triphenylphosphine in tetrahydrofuran with a solution of silver trifluoromethanesulfonate (AgSO₃CF₃) in tetrahydrofuran. It decomposes slowly at room temperature, but can be stored indefinitely at —80°C. IR spectra indicate that a C₅H₅-h⁵-group is present in the molecule and this conclusion is confirmed by ¹H and ¹³C NMR spectroscopy.     

Benzoylation of methyl acrylate. Crystal and molecular structure of (methyl-3-benzoylacrylate)bis(triphenylphosphine)nickel(0)benzene (1:1) solvate

Summary The benzoylation of methyl acrylate with benzoyl chloride and zerovalent nickel has been studied and an x-ray structural analysis of the intermediate (PPh₃)₂Ni(C₁₁H₁₀O₃) · C₆H₆ complex solvate (1:1) has been carried out. The crystals are triclinic with unit cell dimensions:a 12.488(5),b 20.569(7),c 9.733(4)Å; 9().08(5), 65.54(5), 75.85(5)°; space group P ; finalR factor 0.040. The nickel is in a trigonal environment and the olefinic fragment of the methyl 3-benzoylacrylate involved in the coordination is twisted from the plane formed by the metal and the phosphorus by 8.5°. An expected C=C lengthening in the organic ligand is observed.     

Photoluminescence studies of iodobis-(tricyclohexylphosphine)copper(I) and iodobis-(tricyclohexylphosphine)copper(I) benzene solvate

Two newly prepared complexes were found to exhibit strong solid state emission behavior. The complexes are iodobis-(tricyclohexylphosphine)copper(I) and iodobis-(tricyclohexylphosphine)copper(I) benzene solvate. To understand the emission behavior of these complexes, density functional theory (DFT) calculations were employed. These calculations allowed the identification of major atomic contributions to HOMO, LUMO and LUMO+n orbitals. The excitation mechanism was found to be a combination of ligand to metal charge transfer (LMCT) and metal to ligand charge transfer (MLCT), with the dominance of the former. The emission lifetimes were also investigated and the decays of the complexes were found to be a bi-exponential in both methanol and cyclohexane.