Applied Organometallic Chemistry

Organometallic preparation of mono- and multimetallic catalytic systems demonstrate the high potential of nanostructured colloidal materials for the fuel cell application. The colloids obtained from the organometallic pathway are isolable as re-dispersible dry powders, with high metal content, giving long-term stable colloids. These colloids were found as an excellent catalytic precursor for the electrochemical applications.

This review introduces an advance on copper-catalyzed/mediated CH functionalization. The content includes aromatic ring CH bond functionalization and heteroaromatic CH bond functionalization forming new carbon– carbon or carbon– heteroatom bonds.

Chelating dicarbene complexes of palladium(II) and platinum(II) efficiently catalyse the hydroarylation of ethyl phenylpropiolate with aromatic heterocycles.

2,3,4-Unsubstituted quinolines were synthesized from nitroarenes and tris (3-hydroxypropyl)amine via heterogeneous PdC-catalyzed sequence involving reductive alkanol group transfer, N-alkylation and cyclization. The presence of SnCl₂ is essential for the formation of quinolines, although an aqueous medium (H₂O–dioxane) is also necessary for the effective formation of quinolines.

Novel synthetic protocols for the synthesis of lipophilic carboranes have been developed utilizing two CC bond-forming reactions, namely Baylis-Hillman and enynedioate cycloaddition reactions. Some of these carboranes were converted into further functionalized carboranes via nucleophilic allylic isomerization.

Ruthenium(II) hydrazone Schiff base complexes were prepared and characterized. Their application as catalysts in the field of oxidation of alcohols using NMO and molecular oxygen as oxidants and aryl–aryl coupling was studied. Antimicrobial properties of the above complexes were also examined.

Two nickel(II) complexes bearing pyrazolylimine ligand were synthesized and characterized; the solid-state structure of complex 1 was confirmed by X-ray single-crystal analysis. Activated by methylaluminoxane, the two complexes are capable of catalyzing the polymerization of norbornene with moderate activities. The analytical results of polymer structures indicate that the norbornene polymerization is vinyl-type polymerization rather than ROMP.

1,3-Diynes were obtained in high yields by the oxidative homocoupling reactions of terminal alkynes in toluene at 60 °C in air catalyzed by CuCl-piperidine.

Mixed sulfur donor ligand complexes of the type bismuth(III) bis(N,N′-dialkyldithiocarbamato)alkylenedithiophosphate were synthesized in 1:1 molar ratio of chlorobismuth(III) bisdialkyldithiocarbamate and ammonium alkylenedithiophosphate in refluxing benzene and characterized by physicochemical and spectral [UV, IR, NMR (¹H,¹³C and ³¹P) and powder X-ray diffraction] studies. Based on the above-mentioned studies, a tentative structure of these newly synthesized complexes has been assigned. These complexes have been also screened for their antimicrobial activities. The results are indeed positive and exhibit good antibacterial effects.

Enantioselectivities up to 93% ee have been obtained in palladium-catalysed asymmetric allylic alkylation of 1,3-diphenylallyl acetate with amido-phosphanes possessing one to three planar-chiral (S_p)-2-(diphenylphosphanyl)ferrocen-1-yl pendant groups as the ligands.

The electronic spectra of the Cu(II) heterochelates show a broad band in the region of ∼15, 000 cm⁻¹ consistent with that reported for octahedral geometry and, thus, can reasonably be assigned to the ²E_g → ²T_2g transition. Magnetic moment values in the range 1.81–1.82 B.M. also correspond to an octahedral environment around the Cu(II) ion.

The amminolysis reaction promotes the substitution of the chloride by diethylamine group N(C₂H₅)₂. The released chloride will react with the C₂H₅ group to lead to chloroethane (b.p. = 12.5°C).