Three pyridyl‐amide substituted (benz)imidazolium salts H2L1Cl, H2L2Cl and H2L3Cl were synthesized and successfully employed as ligand precursors for the syntheses of novel nickel(II) and cobalt... Show moreThree pyridyl‐amide substituted (benz)imidazolium salts H2L1Cl, H2L2Cl and H2L3Cl were synthesized and successfully employed as ligand precursors for the syntheses of novel nickel(II) and cobalt(III) complexes. The compounds H2L1Cl and H2L2Cl are precursors to tetradentate ligands and differ in the nature of the N‐heterocyclic carbene (NHC) functionality, being imidazole‐based and benzimidazole‐based, respectively. The ligand precursor H2L3Cl resembles H2L1Cl, but with one of the pyridyl groups replaced with a benzyl group, thus yielding a potential tridentate ligand. The nickel(II) compounds [Ni(L1)]Cl and [Ni(L2)]PF6 were obtained, bearing tetradentate ligands comprising an amidate and two pyridine nitrogen donor atoms and an (NHC) carbon donor. Single crystal X‐ray crystallography revealed that the nickel ions in both compounds are in slightly distorted square‐planar geometries. Reactions of cobalt salts with the ligands H2L1Cl and H2L3Cl resulted in the cobalt(III) compounds [Co(L1)2]Cl and [Co(L3)2]PF6; the cobalt ions in both complexes are in octahedral geometries, bound by two tridentate ligands in a meridional binding mode, with two dangling pyridine and benzyl groups, respectively. The four compounds show electrocatalytic activity in proton reduction in dimethylformamide solutions in presence of acetic acid; their activity is compared using cyclic voltammetry and quantified with gas chromatography. Show less
In this thesis two subjects are treated. The first one is the poisoning of hydrogen dissociation on Pt(533) by CO. It was found that decorating the step edges of Pt(533) by CO does not only block... Show moreIn this thesis two subjects are treated. The first one is the poisoning of hydrogen dissociation on Pt(533) by CO. It was found that decorating the step edges of Pt(533) by CO does not only block the indirect dissociation mechanism and the direct dissociation at step edges but also introduces an additional barrier for dissociation at the terraces. The second area contains a description of how a cylindrical Ni single crystal is employed in dissociation dynamics measurements. The analysis of the circumference by LEED is explained. Results for hydrogen dissociation are shown. They are analyzed by means of a model introduced for hydrogen dissociation on stepped Pt surfaces with (111) terraces and (100) steps. Show less
As nickel and platinum are in the same group of the periodic table, the Ni(111) and Pt(111) surfaces may be expected to show similar interaction with water and hydrogen. However in this thesis, we... Show moreAs nickel and platinum are in the same group of the periodic table, the Ni(111) and Pt(111) surfaces may be expected to show similar interaction with water and hydrogen. However in this thesis, we show these interactions for Ni(111) are quite different from those of Pt(111). Moreover, our results show that the Ni(111) surface is a unique surface with regards to its chemistry of water and hydrogen. Show less
Described in this thesis are the investigations into the chemistry of N-heterocyclic carbene (NHC) ligands and transition-metal complexes thereof. Specifically, a variety of N-heterocyclic carbene... Show moreDescribed in this thesis are the investigations into the chemistry of N-heterocyclic carbene (NHC) ligands and transition-metal complexes thereof. Specifically, a variety of N-heterocyclic carbene complexes of nickel were prepared, characterized and used as catalysts in three types of homogeneous catalytic processes. First, nickel(II) complexes of monodentate NHC ligands were successfully used as catalysts in the hydrosilylation of internal alkynes. Second, nickel(II) complexes bearing bidentate N-heterocyclic carbene ligands or functionalized NHC ligands were shown to be highly effective in the Kumada coupling of aryl halides with aryl Grignard reagents. In addition, the nickel-catalyzed Kumada coupling was investigated using quantum-chemical calculations. Finally, all three types of nickel complex were tested for their catalytic activity in the vinyl polymerization of norbornene. Furthermore, a silv er(I) NHC complex was isolated, characterized and used in the preparation of a nickel(II) NHC complex. Show less
