Yttrium Complexes Featuring Different Y-C Bonds. Comparative Reactivity Studies: Toward Terminal Imido Complexes (Articolo in rivista)

Type
Label
  • Yttrium Complexes Featuring Different Y-C Bonds. Comparative Reactivity Studies: Toward Terminal Imido Complexes (Articolo in rivista) (literal)
Anno
  • 2013-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1021/om400099z (literal)
Alternative label
  • Alexander A. Karpov, Anton V. Cherkasov, Georgy K. Fukin, Andrei S. Shavyrin, Lapo Luconi, Giuliano Giambastiani, Alexander A. Trifonov (2013)
    Yttrium Complexes Featuring Different Y-C Bonds. Comparative Reactivity Studies: Toward Terminal Imido Complexes
    in Organometallics (Online); ACS, American chemical society, Washington, DC (Stati Uniti d'America)
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Alexander A. Karpov, Anton V. Cherkasov, Georgy K. Fukin, Andrei S. Shavyrin, Lapo Luconi, Giuliano Giambastiani, Alexander A. Trifonov (literal)
Pagina inizio
  • 2379 (literal)
Pagina fine
  • 2388 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume
  • 32 (literal)
Rivista
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#pagineTotali
  • 10 (literal)
Note
  • Scopus (literal)
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  • G. A. Razuvaev Institute of Organometallic Chemistry of the Russian Academy of Sciences, Tropinina 49, GSP-445, 603950 Nizhny Novgorod, Russia Institute of Chemistry of OrganoMetallic Compounds, ICCOM-CNR, Via Madonna del Piano, 10, 50019 Sesto Fiorentino (Florence), Italy (literal)
Titolo
  • Yttrium Complexes Featuring Different Y-C Bonds. Comparative Reactivity Studies: Toward Terminal Imido Complexes (literal)
Abstract
  • The reactions of 2,6-diisopropylaniline with equimolar amounts of alkyl-heteroaryl yttrium complexes containing Y-C(sp3, alkyl) along with Y-C(sp2, heteroaryl) bonds resulting from intramolecular C-H bond activation of the amido-pyridinate ligands [NNOBzFur]YCH2SiMe3(THF)2, [NNSBzTh]YCH2SiMe3(THF)2, and [NNSEtTh]YCH2SiMe3(THF)2 have been scrutinized with the aim of synthesizing yttrium terminal imido species. These reactions occur at ambient temperature with the protonolysis of the Y-C(sp3,alkyl) bond, thus affording anilido-heteroaryl species and maintaining the residual Y-C(sp2, heteroaryl) bond untouched. However, the subsequent transformation of the as-synthesized anilido-heteroaryl complexes depends on the nature of the substituent on the 6-position of the pyridyl ring. In the case of the benzofuryl yttrium derivative [NNOBzFur]YNH-2,6-iPr2C6H3(THF)2 (4), heating to 50 °C results in benzofuran ring opening with the formation of an anilido species supported by a dianionic amido-yne-phenolate ligand framework, [NNC=CO]YNH-2,6-iPr2C6H3(THF) (6). In contrast, a complex containing a benzothiophenyl moiety, [NNSBzTh]YNH-2,6-iPr2C6H3(THF)2 (7), slowly undergoes protonation of the Y-C(sp2, heteroaryl) bond and a ligand redistribution reaction takes place, affording an yttrium bis(anilido) species supported by a monoanionic amido-pyridinate ligand featuring intramolecular Y-S heteroaryl coordination, [NNSBzTh]Y[NH-2,6-iPr2C6H3]2 (9). It is worth noting that an yttrium complex containing ?-thiophenyl fragment, [NNSEtTh]YNH-2,6-iPr2C6H3(THF)2 (10), turned out to be extraordinarily robust and no transformation was ever detected even upon heating the complex at 100 °C for prolonged times. (literal)
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