PUB - Publikationen an der Universität Bielefeld

The synthesis of nickel, palladium and platinum complexes with the 1-dimethylaminaethyl-2,3,4,5-tetramethylcycolpentadienyl (Cp^) ligand is described. The reaction of Ni(CO)(4) with (C(5)Me(4)CH(2)CH(2)NMe(3))Li (1) and CuCl leads to the formation of the dimeric nickel(I) complex [(C(5)Me(4)CH(2)CH(2)NMe(2))(2)Ni-2(CO)(2)] (2). The structure of 2 has been determined by single-crystal X-ray diffractometry. Complex 2 reacts with 2 equiv. of HBF4 under protonation of the amino groups to give the compound [(C(5)Me(4)CH(2)CH(2)N(H)Me(2))(2)Ni-2 (Co)(2)](2+) [2BF(4)](2-) (3), which shows excellent solubility in polar solvents. The complex [(C(5)Me(4)CH(2)CH(2)NMe(3))(2)Ni-2(CO)(2)](2+) [2I](2-) (4) with two quaternary dimethylamino groups is prepared by the reaction of 2 with 2 equiv, of Mel. Oxidative cleavage of 2 with iodine in the presence of PMe(3) leads to the formation of the nickel(II) complex [(C(5)Me(4)CH(2)CH(2)NMe(2))Ni(PMe(3))I] (5). Reaction of [Pd(CO)Cl](n) with [(C(5)Me(4)CH(2)CH(2)NMe(2))MgCl](2) gives the thermally labile palladium(I) complex [(C(5)Me(4)CH(2)CH(2)NMe(2))(2)Pd-2(CO)(2)] (6) in a mixture with Cp^H. The thermally labile palladium(II) complex [(C(5)Me(4)CH(2)CH(2)NMe(2))PdC3H5] (7) is obtained by the reaction of [(C3H5)PdCl](2) with [C(5)Me(4)CH(2)CH(2)NMe(2)]Li and characterized only by H-1 and C-13 NMR spectroscopy. The platinum complex [(C(5)Me(4)CH(2)CH(2)NMe(2))Pt(IV)Me(3)] (8) is formed in the reaction of [IPtMe(3)](4) with [C(5)Me(4)CH(2)CH(2)NMe(2)]Li (1). Compound 8 reacts with 1 equiv. of HBF4 to form [(C(5)Me(4)CH(2)CH(2)N(H)Me(2))Pt(IV)Me(3)](+) BF4- (9) with a protonated amino group which leads to good solubility in polar solvents. In the reaction of 8 with 2 equiv. of HBF4, the cyclopentadienyl-platinum-fluoro complex (C(5)Me(4)CH(2)CH(2)N(H)Me(2))Pt(IV)Me(2)F](+) BF4- (10) is formed.