Abstract
M.Sc.
Several bis[1-ferrocenyl(ethyl)pyrazolyl palladium dichloro (complexes 1 and 3) and palladium
chloromethyl complexes (complexes 2 and 4) have been synthesized by the reactions of 1-
ferrocenyl(ethyl)-1N-pyrazole and 1-ferrocenyl(ethyl)-1N-(3,5-dimethyl)pyrazole with
[PdCl2(NCMe)2] and [PdClMe(cod)] respectively.
Furthermore, a library of phosphorus^nitrogen (P^N) ferrocenyl(ethyl)-amine and -pyrazolyl ligands
have been successfully synthesized using the well known Ugi amine (compound 5) as intermediate. 1-
[2-{diphenylphosphino}ferrocenyl](ethyl)amine and 1-[{2-diphenylphosphino}ferrocenyl](ethyl)-
pyrazolyl Ni(II) and Pd(II) complexes were synthesized by reacting 1-[2-
{diphenylphosphino}ferrocenyl](ethyl)dimethylamine, 1-[2-{diphenylphosphino}ferrocenyl](ethyl)-
1N-pyrazole and 1-[2-{diphenylphosphino}ferrocenyl](ethyl)-1N-(3,5-dimethyl)pyrazole with
[NiCl2•6H2O] (compounds 12 and 16), [NiBr2(DME)] (compounds 13, 17 and 19), [PdCl2(NCMe)2]
(compounds 10, 14, and 18) and [PdClMe(cod)] (compounds 11 and 15), respectively. 1-[2-
{Diphenylphosphino}ferrocenyl(ethyl)-1N-(3,5-dimethyl)pyrazole (compound 9) was synthesized by
two distinct methodologies. In one method, 1-ferrocenyl(ethyl)dimethylamine was converted to 1-[2-
{diphenylphosphino}ferrocenyl](ethyl)dimethylamine before it was subsequently reacted with 3,5-
dimethylpyrazole to produce 1-[2-{diphenylphosphino}ferrocenyl(ethyl)-1N-(3,5-dimethyl)pyrazole.
In the other method, 1-ferrocenyl(ethyl)-1N-(3,5-dimethyl)pyrazole was converted to 1-[2-
{diphenylphosphino}ferrocenyl](ethyl)-1N-(3,5-dimethyl)pyrazole before the reaction with 3,5-
dimethylpyrazole, producing 1-[2-{diphenylphosphino}ferrocenyl(ethyl)-1N-(3,5-dimethyl)pyrazole.
These compounds synthesized via different methods as well as their palladium dichloro complexes
show different structures in solution, but solid state structural analysis agrees on the same structure.
The structural difference in solution is contributed to the high degree of flexibility at the stereogenic
centre of the complex.
The Ni(II) ferrocenyl phosphine complexes 12, 13, 16, 17 and 19 exist in equilibrium between
diamagnetic square planar form and paramagnetic tetrahedral form. The tetrahedral geometry is
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favoured over the square planar geometry, purely on steric grounds, but the square planar geometry
occurs with d8 complexes because of the more favourable electronic situation of the complex.
Activation of these P^N palladium and nickel ferrocenyl- amine and -pyrazolyl pre-catalysts 10, 12,
13, 14, 16, 17, 18a and 19 with EtAlCl2 results in the oligomerization of ethylene to C4 and C6
alkenes, followed by subsequent Friedel-Crafts alkylation of the toluene solvent. Moderate catalytic
activities of up to 659 kg of alkylated toluene products.mol-1 Ni. h-1 were observed for catalyst 13 at
20 bar ethylene pressure. In general, the Ni(II) pre-catalysts were more active than the Pd(II) precatalyst.