Synthesis, Structures, and Reactivity of Yttrium Alkyl and Alkynyl Complexes with Mixed Tp<superscript>Me2</superscript>/Cp Ligands.
In: Inorganic Chemistry, Jg. 50 (2011-11-21), Heft 22, S. 11813-11824
academicJournal
Zugriff:
The structurally characterized TpMe2-supported rare earth metal monoalkyl complex (TpMe2)CpYCH2Ph(THF) (1) was synthesized via the salt-metathesis reaction of (TpMe2)CpYCl(THF) with KCH2Ph in THF at room temperature. Treatment of 1 with 1 equiv of PhC≡CH under the same conditions afforded the corresponding alkynyl complex (TpMe2)CpYC≡CPh(THF) (2). Complex 1 exhibits high activity toward carbodiimides, isocyanate, isothiocyanate, and CS2; treatment of 1 with such substrates led to the formation of a series of the corresponding Y-C(benzyl) σ-bond insertion products (TpMe2)CpY[(RN)2CCH2Ph] (R = iPr(3a), Cy(3b), 2,6-iPr-C6H3(3c)), (TpMe2)CpY[SC(CH2Ph)NPh] (4), (TpMe2)CpY[OC(CH2Ph)NPh] (5), and (TpMe2)CpY(S2CCH2Ph) (6) in 40-70% isolated yields. Carbodiimides and isothiocyanate can also insert into the Y-C(alkynyl) σ bond of 2 to yield complexes (TpMe2)CpY[(RN)2CC≡CPh] (R = iPr(7a), Cy(7b)) and (TpMe2)CpY[SC(C≡CPh)NPh] (9). Further investigation results indicated that 1 can effectively catalyze the cross-coupling reactions of phenylacetylene with carbodiimides. However, treatment of o-allylaniline with a catalytic amount of 1 gave only the benzyl abstraction product (TpMe2)CpY(NHC6H4CH2CH-CH2-o)(THF) (10), without observation of the expected organic hydroamination/cyclization product. All of these new complexes were characterized by elemental analysis and spectroscopic properties, and their solid-state structures were also confirmed by single-crystal X-ray diffraction analysis. [ABSTRACT FROM AUTHOR]
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Synthesis, Structures, and Reactivity of Yttrium Alkyl and Alkynyl Complexes with Mixed Tp<superscript>Me2</superscript>/Cp Ligands.
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Autor/in / Beteiligte Person: | Yi, Weiyin ; Zhang, Jie ; Li, Meng ; Chen, Zhenxia ; Zhou, Xigeng |
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Zeitschrift: | Inorganic Chemistry, Jg. 50 (2011-11-21), Heft 22, S. 11813-11824 |
Veröffentlichung: | 2011 |
Medientyp: | academicJournal |
ISSN: | 0020-1669 (print) |
DOI: | 10.1021/ic2019499 |
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