Lanthanide-mediated ligand transfer reactions--a route to late transition metal bisamido complexes

The reaction of [[O(SiMe2Ap)2)2LnLi(thf)n] 1 (Ln = Nd, n= 2) and 2 (Ln = La, n = 3) in hexane with [(dme)NiCl2] (dme = dimethoxyethane) and [(cod)PtCl2] (cod = 1,5-cyclooctadiene) leads to the dimeric Ni complex [[O(SiMe2Ap)2]2Ni2] (3) and the mononuclear platinum compound [O(SiMe2Ap)2Pt] (4). respectively (O(SiMe2ApH)2 = bis(4-methyl-2-pyridylamino)tetramethyldisiloxane). Compounds 3 and 4 have been characterized by X-ray crystal structure analysis. The ligand-transfer reactions probably proceed via heterobimetallic intermediates. A model complex of such an intermediate [[O(SiMe2Ap)2)2NdPdMe] (7) was isolated by reacting 1 with [(cod)PdMeCl]. Applications of complex 3 in ethylene oligomerization were investigated. Highly branched oligomers with a very narrow molecular weight distribution (Mn =230 gmol(-1) (relative to polystyrene standards), Mw/M= 1.14) are produced when Et3Al2Cl3 is employed as a co-catalyst and CH2Cl2 as the solvent (TOF = 122000 h(-1). Treatment of one equivalent of 1 or 2 with two equivalents of [(cod)CuCl] results in the formation of the polycyclic tetranuclear complex [[O(SiMe2Ap)2]2Cu4] (8). An X-ray crystal structure analysis of 8 shows channels formed by a series of fourteen-membered rings in the solid state.