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  Benzonitrile Adducts of Terminal Diarylphosphido Complexes: Preparative Sources of “Ru═PR2

Hoyle, M.-A.-M., Pantazis, D. A., Burton, H. M., McDonald, R., & Rosenberg, L. (2011). Benzonitrile Adducts of Terminal Diarylphosphido Complexes: Preparative Sources of “Ru═PR2”. Organometallics, 30(23), 6458-6465. doi:10.1021/om200822e.

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 Urheber:
Hoyle, Marc-André M.1, Autor
Pantazis, Dimitrios A.2, Autor           
Burton, Hannah M.1, Autor
McDonald, Robert3, Autor
Rosenberg, Lisa1, Autor
Affiliations:
1Department of Chemistry, University of Victoria, P.O. Box 3065, Victoria, British Columbia, Canada V8W 3V6, ou_persistent22              
2Research Department Neese, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society, ou_3023879              
3X-ray Crystallography Laboratory, Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada T6G 2G2, ou_persistent22              

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 Zusammenfassung: Dehydrohalogenation of secondary diarylphosphine ruthenium complexes in the presence of benzonitrile yields stable, isolable nitrile adducts of the formula [Ru(η5-indenyl)(PAr2)(NCPh)(PPh3)], in which the terminal phosphido ligand is pyramidal at P and contains a stereochemically active lone pair. Unlike the analogous carbonyl adducts [Ru(η5-indenyl)(PAr2)(CO)(PPh3)], these benzonitrile complexes behave as masked sources of the highly reactive planar phosphido complexes [Ru(η5-indenyl)(PAr2)(PPh3)], which contain a Ru═PAr2 π bond. This is illustrated by the addition (or cycloaddition) reactions of the benzonitrile adducts with dihydrogen, methyl iodide, and 1-hexene, as well as their thermal decomposition via orthometalation of the PPh3 ligand. Enthalpies of CO vs NCPh dissociation from the [Ru(η5-indenyl)(PR2)(PPh3)] fragments (R = alkyl, aryl) have been calculated, as has the trajectory of addition of H2 to the model planar phosphido complex [Ru(η5-indenyl)(PMe2)(PMe3)]. The latter study shows the intermediacy of an η2-H2 adduct, [Ru(η5-indenyl)(PAr2)(η2-H2)(PPh3)], in the formation of [RuH(η5-indenyl)(HPMe2)(PMe3)], a further indication of the importance of the variable binding modes of the terminal phosphido ligand in this system.

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Sprache(n): eng - English
 Datum: 2011-09-012011-11-072011-12-12
 Publikationsstatus: Erschienen
 Seiten: 8
 Ort, Verlag, Ausgabe: -
 Inhaltsverzeichnis: -
 Art der Begutachtung: Expertenbegutachtung
 Identifikatoren: DOI: 10.1021/om200822e
 Art des Abschluß: -

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Titel: Organometallics
  Andere : Organometallics
Genre der Quelle: Zeitschrift
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Ort, Verlag, Ausgabe: Washington, D.C. : American Chemical Society
Seiten: - Band / Heft: 30 (23) Artikelnummer: - Start- / Endseite: 6458 - 6465 Identifikator: ISSN: 0276-7333
CoNE: https://pure.mpg.de/cone/journals/resource/954925505259