Oxalamidinate complexes

Oxalamidinate anions represent the most simple type of bis(amidinate) ligands in which two amidinate units are directly connected via a central C-C bond. Oxalamidinate complexes of d-transition metals have recently received increasing attention for their efficient catalytic activity in olefin polymerization reactions. Almost all the oxalamidinate ligands have been synthesized by deprotonation of the corresponding oxalic amidines [pathway (a) in Scheme 190]. More recently, it was found that carbodiimides, RN = C=NR, can be reductively coupled with metallic lithium into the oxalamidinate dianions [(RN)2C-C(NR)2] [route (c)J which are clearly useful for the preparation of dinuclear oxalamidinate complexes. The lithium complex obtained this way from N,N -di(p-tolyl)carbodiimide was crystallized from pyridine/pentane and... 

Treatment of UCI4 with the lithium complex obtained from dicyclohexylcar-bodiimide followed by crystallization from pyridine afforded a dinuclear uranium(rV) oxalamidinate complex in the form of dark green crystals in 94% yield (Scheme 191). The same compound could also be obtained by first reducing UCI4 to LiUCli (or UQs+LiCl) followed by reductive dimerization of di(cyclo-hexyl)carbodiimide as shown in Scheme 191. The molecular structure of this first oxalamidinato complex of an actinide element is depicted in Figure 31. ° ... 

The palladium(ll) and heterobimetallic palladium(ll)/zinc oxalamidinate complexes depicted in Scheme 197 have been prepared analogously from the free ligands and Pd(acac)2 or ZnEt2/Pd(acac)2, respectively ... 

The readily accessible oxalamidine derivative PhN = C(NHBu )C(NHBu ) = NPh provides another useful entry into the coordination chemistry of oxalamidinato ligands. Scheme 195 summarizes the results of an initial study. Mono- and dinuclear complexes of Ti, Zr, and Ta have been isolated and fully characterized. Silylation of both N-H functions was achieved by subsequent treatment with 2 equivalents of n-butyllithium and MesSiCl. The preparation of a nickel(II) complex failed and gave a hydrobromide salt instead. ... 

Both binuclear and trinuclear oxalamidinate palladium complexes were employed by Rau, Walther and coworkers [79] in copper-free Sonogashira reactions. The peculiarity of the system was seen to reside in the presence of chemical bridges that allowed electronic communication between metal centers (Scheme... 

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