Abstract
The first part of this thesis aim for the synthesis of the Low-valent, low-coordinate tetranuclear metal complexes (M = Al, Ni) by the use of tetradentate multinitrogen ligand (2,7-bis(2,4,6-trimethylanilinyl)-1,8-naphthyridine (H2(N2N2)Mes) (Mes = 2,4, 6-Me3C6H2) under mild conditions. We intended to work with free ligand as such. Treatment of H2(N2N2)Mes with AlMe3 and AlEt2Cl produced dinuclear {AlMe[μ-κ4-(N2N2)Mes]}2 (1), {AlCl[μ-κ4-(N2N2)Mes]}2 (3)and{AlEt[μ-κ4-(N2N2)Mes]}2 (4)respectively. Interestingly, reaction of H2(N2N2)Mes with 1.5 equivalents Ni(COD)2, led to the isolation of trinickel lantern-type complex, Ni3[μ3-κ3-(N2N2)Mes]3 (5). Alternatively, 5 can be prepared by the reduction of NiI2(THF)2[κ2-(N2N2)Mes] with 2 equiv. KC8. Complex 5 further reduced with 2 equivalents KC8 to give mono nuclear Ni[κ2-(N2N2)Mes]3 (6). Moreover, a mix-valent trinickel complex Ni3[μ3-κ3-(N2N2)Mes]2[μ-κ2-(N2N2)Mes] (7) was prepared by the reaction of H2(N2N2)Mes with 2.1 equivalents Ni(COD)2. The second part of this thesis highlights trimerization of nitriles by using inverted sandwich vanadium complex. 2,4,6-triphenyltriazine was prepared from PhCN by using (μ-η6:η6-C7H8)[V(Nacnac)]2 (Nacnac = HC(C(Me)NC6H3-iPr2)2) (9) as a catalyst. While investigating the formation mechanism of these triazines, [κ2-(NC(Ph)C(Ph)NC(Ph)N)]V(Nacnac) (10) was isolated from the reaction of 9 with PhCN. Furthermore, reaction of 9 with o-tolunenenitrile, 4-chloro-2-methylbenzonitrile in hexane produced [(o-tolyl)CN]2[κ2-Ht]V(Nacnac) (12) (Ht= (3-(o-tolyl))isoquinolin-1-amine ) and [κ2-ClHt][ClHt]V(Nacnac) (13) (ClHt= 6-chloro-3-(4-chloro-2-methylphenyl)isoquinolin-1-amine.