Insertion of ketenes into lanthanocene n-butylamide and imidazolate complexes |
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| Authors: | Ruiting Liu Pengzhi Zheng Linhong Weng Xigeng Zhou Chunyuan Liu |
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| Affiliation: | 1. Department of Chemistry, Molecular Catalysis and Innovative Material Laboratory, Fudan University, Shanghai 200433, People’s Republic of China;2. State Key Laboratory of Organometallic Chemistry, Shanghai 200032, People’s Republic of China;3. Department of Chemistry, Tongji University, Shanghai 200092, People’s Republic of China;1. Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC 29208, USA;2. Department of Chemistry, Texas A&M University, College Station, TX 77843, USA;3. Department of Chemistry, Purdue University, West Lafayette, IN 47907, USA |
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| Abstract: | Reaction of Cp2LnNHnBu with 1 equiv. of Ph2CCO in toluene affords dimeric complexes [Cp2Ln(OC(CHPh2)NnBu)]2 [Ln = Yb (1), Dy (2)], derived from a formal insertion of the C C bond of the ketene into the N–H bond. Treatment of CpErCl2 with 2 equiv. of LiNHnBu followed by reacting with Ph2CCO affords a rearrangement product [Cp2Er(OC(CHPh2)NnBu)]2 (3). Treatment of [Cp2Ln(μ-Im)]3 (Im = imidazolate) with PhRCCO gives [Cp2Ln(μ-OC(Im)CPhR)]2 [R = Et, Ln = Yb (4); R = Ph, Ln = Yb (5), Er (6)]. In contrast to the previous observations that [Cp2ErNiPr2]2 and [Cp2ErNHEt]2 react with ketenes to give di-insertion products, in the present cases the presence of excess of ketenes has no influence on the final product even with prolonged heating and only monoinsertion products are isolated. All these complexes were characterized by elemental analysis, IR and mass spectroscopies. The structures of complexes 1 and 3–6 were also determined through X-ray single crystal diffraction analysis. |
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