365540-76-7Relevant academic research and scientific papers
Di-, Tri-, and Tetranuclear Complexes of Ni, Pd, and Zn with Oxalamidinato Bridges: Syntheses, Structures and Catalytic Reactions
Walther, Dirk,Doehler, Thomas,Theyssen, Nils,Goerls, Helmar
, p. 2049 - 2060 (2007/10/03)
The reaction of oxalic R1N=C(NHR2)-C(NHR2)=NR1 (oxamH2) with 2 equiv. (allyl)2M or (acac)2M (M: Ni, Pd) results in the formation of dinuclear complexes [(T)M(oxam)M(T)] containing dianionic bridging oxalamidinate and η3-allyl or acac as terminal ligands T. The complexes were characterized by elemental analyses, mass spectrometry, and (1)H and (13)C NMR spectroscopy. In addition, the solid-state structures of 1 (M: Ni; T: η3-allyl; R1 = p-tolyl; R2 = mesityl), 2 (M: Ni; T: η3-allyl; R1 = R2 = mesityl), 9 (M: Pd; T: acac; R1 = phenyl; R2 = p-tolyl), and 10 (M: Pd; T: acac; R1 = R2 = p-tolyl) were determined by X-ray single-crystal diffraction analyses. All complexes contain the metal ions in a squareplanar environment. Furthermore, in the η3-allyl complexes two isomers are found in which the two allyl groups are oriented in syn and anti positions. Trinuclear complexes of the composition [(T)M(oxam)M1(oxam)M(T)] (M1: Zn; M: ni or Pd) are obtained by treating Et2Zn with 2 equiv. of an oxalic amidine in toluene, followed by addition of 2 equiv. M(acac)2 or Pd(allyl)2. The synthesis andd solid-state X-ray analysis of the tetranuclear complex [(T)M(oxam)M1(oxam)M(T)] (16: M = M1: Zn; oxam: R1 = p-tolyl; R2 = mesityl) is also described. A number of NiII complexes oligomerize or polymerize ethylene upon activation with MaO or Et3Al. The catalyses can be adjusted by the bulkiness of the nitrogen substituents, the nature of thee cocatalyst, and the nuclearity of the complexes. The most active and selective polymerization catalyst is the heterotrinuclear NiZnNi complex 12 which contains two tetraamesityloxalamidinato bridges and acac as terminal ligands T. Complex 12 can be activated by using only 2 equiv. Et3Al per Ni. Initial efforts show that the palladium complexes are catalysts for the Heck coupling.
