723293-49-0Relevant academic research and scientific papers
Insertion of a carbodiimide into the Ln-N σ-bond of organolanthanide complexes. Isomerization and rearrangement of organolanthanides containing guanidinate ligands
Zhang, Jie,Cai, Ruifang,Weng, Linhong,Zhou, Xigeng
, p. 3303 - 3308 (2004)
The reaction of (C5H5)YCl2(THF) 3 with LiNiPr2 and subsequently with 2 equiv of N,N-diisopropylcarbodiimide (iPrN=C=NiPr) in THF gave the organoyttrium guanidinates Y[iPrNC(NiPr 2)NiPr]3 (1) and (C5H 5)2Y[iPrNC(NiPr2)N iPr] (2), which may be rationalized by the rearrangement reaction of the diinsertion product (C5H5)Y[iPrNC(N iPr2)N'Pr]2. Treatment of iPrN-C=N iPr with lanthanocene primary amides [(C5H 5)2LnNHR]2 (R = tBu, Ln = Yb, Er, Dy, Y; R = Ph, Ln = Yb) gave the unexpected products (C5H 5)2Yb[RNC(NHiPr)NiPr] (R = tBu, Ln = Yb (3), Er (4), Dy (5), Y(6); R = Ph, Ln = Yb (7)), indicating that a novel isomerization reaction involving a 1,3-hydrogen shift takes place along with the insertion of carbodiimide into the Ln-N a-bond, which provides an efficient synthesis of organolanthanide complexes with asymmetrical guanidinate ligands. All these complexes were characterized by elemental analysis and spectroscopic properties. The structures of complexes 1-5 and 7 were also determined by X-ray diffraction analysis.
