Synthesis and Reactivity of Indenyl Ruthenium Complexes with the Labile Ligand 1,5-Cyclooctadiene: Catalytic Activity of [Ru(C9H7)Cl(COD)] (Articolo in rivista)

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  • Synthesis and Reactivity of Indenyl Ruthenium Complexes with the Labile Ligand 1,5-Cyclooctadiene: Catalytic Activity of [Ru(C9H7)Cl(COD)] (Articolo in rivista) (literal)
Anno
  • 2001-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1021/om010205w (literal)
Alternative label
  • Patricia Alvarez, Jose´ Gimeno, Elena Lastra, Santiago Garcia-Granda, Juan Francisco Van der Maelen, Mauro Bassetti (2001)
    Synthesis and Reactivity of Indenyl Ruthenium Complexes with the Labile Ligand 1,5-Cyclooctadiene: Catalytic Activity of [Ru(C9H7)Cl(COD)]
    in Organometallics; ACS, American chemical society, Washington, DC (Stati Uniti d'America)
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Patricia Alvarez, Jose´ Gimeno, Elena Lastra, Santiago Garcia-Granda, Juan Francisco Van der Maelen, Mauro Bassetti (literal)
Pagina inizio
  • 3762 (literal)
Pagina fine
  • 3771 (literal)
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  • 20 (literal)
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  • 10 (literal)
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  • ISI Web of Science (WOS) (literal)
  • Scopus (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • Departamento de Quimica Organica e Inorganica, Facultad de Qu?mica, Universidad de Oviedo, Instituto de Qu?mica Universitaria \"Enrique Moles\" (Unidad Asociada al CSIC), 33006 Oviedo, Spain; Departamento de Qu?mica F?sica y Anal?tica, Facultad de Qu?mica, Universidad de Oviedo, 33006 Oviedo, Spain; Centro CNR di Studio sui Meccanismi di Reazione, c/o Dipartimento di Chimica, Universita´ \"La Sapienza\", 00185 Roma, Italy (literal)
Titolo
  • Synthesis and Reactivity of Indenyl Ruthenium Complexes with the Labile Ligand 1,5-Cyclooctadiene: Catalytic Activity of [Ru(C9H7)Cl(COD)] (literal)
Abstract
  • The treatment of [RuCl2(COD)]n with KC9H7 in THF leads to the formation of [Ru(eta-5- C9H7)Cl(COD)] (1) (80% yield) in a one-pot synthesis. Complex 1 is also formed by the reaction of [RuCl2(COD)]n with NaC9H7 in THF followed by treatment of the intermediate complex [Ru(eta-5-C9H7)(eta-2-eta-3-C8H11)] (2) with HCl. Substitution of the labile COD ligand by bulky phosphines PR3 (R ) Cy, iPr3) can be achieved at room temperature in THF to give 16- electron species [Ru(eta-5-C9H7)Cl(PR3)], which react with CO (1 atm) to afford complexes [Ru(eta-5-C9H7)Cl(CO)(PR3)] (R ) Cy (3a), iPr (3b)). Chelate complexes [Ru(eta-5-C9H7)Cl{( 2-P,N)- o-Ph2PC6H4C(H)dNtBu}] (4) and [Ru(è4-C9H7){ 1-(P)-Ph2PCH2C(O)tBu}{ 2-(P,O)Ph2PCHd C(O)tBu}] (5) have been similarly prepared by reaction with the bidentate ligands. [Ru(eta-5- C9H7)Cl(NBD)] (NBD ) norbornadiene) (6) has been prepared through an exchange reaction of 1 with NBD and characterized by X-ray diffraction. Neutral complexes [Ru(eta-5-C9H7)X- (COD)] (X ) FBF3 (7), N3 (8)) were prepared from complex 1 by metathesis reactions of the chloride ligand by AgBF4 and NaN3 respectively. The treatment of 7 in CH2Cl2 with an excess of pyridine and acetonitrile gives cationic complexes [Ru(eta-5-C9H7)(COD)L][BF4] in good yield (L ) py (9), CH3CN (10)). The structure of complex 9 has been determined by X-ray diffraction. Complex 1 catalyzes [2+2] and [4+2] cycloaddition reactions of norbornene and 1,5-cyclooctadiene with alkynes to give exotricyclic [4.2.1.0] coupling products and exotricyclo [4.2.2.0]dec-7-enes, respectively. These processes take place with high efficiency and selectivity. Complex 1 is also active in the catalytic hydration of terminal alkynes to afford ketones in high yield and selectivity. (literal)
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