Dissertation

|4 Summary|
10
[TEA] +
TEA
visible
light
N
N
e - H 2
N Cl
N
2+ Pt
N
N Cl
Ru
2 H +
N
N
Ru
TON / mol H2 /mol Cat
8
6
4
2
0
0 5 10 15 20
Irradiation time / h
5. The development of new procedures was used to create the new ligands bip and the imidazolium
salt bbip in a stepwise synthesis (method L2 and L3) from ip. Elemental analysis,
mass spectrometry, different NMR techniques and, importantly, X-ray diffraction were used
for the characterization of the new bridging ligand and its precursors. NMR studies were used
to trace and fit the H/D-exchange kinetics of the active N-CH-N-proton at the imidazolium
salt in methanol-d 4 , whereat a rate constant of k = 2.36×10 -5 s -1 and a half life of t 1/2 = 490 min
were determined. The results indicate that bbip successfully combines two important ligand
motifs, a phenanthroline- and a NHC-type coordination sphere.
6. Off the ip-ligands, the series of mononuclear ruthenium complexes Ru(ip), Ru(bip), and
Ru(bbip), carrying the {Ru(tbbpy) 2 } 2+ -fragment, was prepared. The resulting complexes
were fully characterized, but particular attention was paid to solid state structural analysis,
absorption and emission behavior, and electrochemical behavior.
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