A new
family of lanthanide complexes with di- and triphenylacetate
ligands was prepared from LnCl3. Dimeric diphenylacetates
were the only isolated products of the reaction between LnCl3 (Ln = La, Nd) and Ph2CHCOONa. The exchange reaction between
LnCl3 and Ph3CCOONa led to the formation of
three structurally different types of neodymium and lanthanum complexes
under different reaction conditions. Various coordination modes of
the carboxylate ligands were revealed, including κ2- and κ1-terminal coordination, μ2-κ1:κ1-bridging, and μ2-κ1:κ2-semibridging. The
treatment of La and Nd tris-triphenylacetates with excess AlEt3 produces the dimeric tetraethylaluminates [Ln2((μ2-κ1:κ1-Ph3CCOO)4(AlEt4)2]. The structures
of the key La and Nd triphenylacetates that were obtained from these
reactions were verified by X-ray diffraction, and the complex [(THF)4Nd2(Ph2CHCOO)2(μ2-κ1:κ2-Ph2CHCOO)2(μ2- κ1:κ1-Ph2CHCOO)2] was studied by high-resolution
X-ray diffraction. Neodymium di- and triphenylacetate complexes can
serve as precursors of catalysts for butadiene and isoprene stereospecific
1,4-cis polymerization.
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