Deutsch
 
Benutzerhandbuch Datenschutzhinweis Impressum Kontakt
  DetailsucheBrowse

Datensatz

DATENSATZ AKTIONENEXPORT

Freigegeben

Zeitschriftenartikel

(R2PC2H4PR2)Pd0−1-Alkyne Complexes

MPG-Autoren

Schager,  Frank
Max-Planck-Institut für Kohlenforschung, Max Planck Society;

Bonrath,  Werner
Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons58898

Pörschke,  Klaus-Richard
Research Group Pörschke, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

Kessler,  Magnus
Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons58723

Krüger,  Carl
Service Department Krüger (XRAY), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

Seevogel,  Klaus
Max-Planck-Institut für Kohlenforschung, Max Planck Society;

Externe Ressourcen
Es sind keine Externen Ressourcen verfügbar
Volltexte (frei zugänglich)
Es sind keine frei zugänglichen Volltexte verfügbar
Ergänzendes Material (frei zugänglich)
Es sind keine frei zugänglichen Ergänzenden Materialien verfügbar
Zitation

Schager, F., Bonrath, W., Pörschke, K.-R., Kessler, M., Krüger, C., & Seevogel, K. (1997). (R2PC2H4PR2)Pd0−1-Alkyne Complexes. Organometallics, 16(20), 4276-4286. doi:10.1021/om9702035.


Zitierlink: http://hdl.handle.net/11858/00-001M-0000-0024-4C65-1
Zusammenfassung
Displacement of the ethene ligand in (dippe)Pd(C2H4) (dippe = iPr2PC2H4PiPr2) by 1-alkynes RC⋮CH affords the mononuclear complexes (dippe)Pd(RC⋮CH) (R = Me (2a), Ph (3a), CO2Me (4), SiMe3 (5)). The molecular structure of 3a has been determined by X-ray crystallography. Mononuclear 2a and 3a have been reacted with stoichiometric amounts of (dippe)Pd(η1-C3H5)2 as a source for [(dippe)Pd0] to yield the dinuclear derivatives {(dippe)Pd}2(μ-RC⋮CH) (R = Me (2b), Ph (3b)). By the reaction of (dippe)Pd(C2H4) with difunctional vinylacetylene the mononuclear complex (dippe)Pd{(1,2-η2)-RC⋮CH} (R = CHCH2 (6a)) is formed, which is in equilibrium with isomeric (dippe)Pd{(3,4-η2)-H2CCHC⋮CH} (6b). Addition of [(dippe)Pd0] to 6a,b yields dinuclear {(dippe)Pd}2(μ-RC⋮CH) (R = CHCH2 (6c)). Reaction of (dippe)Pd(C2H4) with butadiyne affords (dippe)Pd(η2-HC⋮CC⋮CH) (7c). From dippe, Pt(cod)2, and C4H2 the Pt homologue has also been synthesized and thus, together with the already known Ni derivative, the series (dippe)M(η2-HC⋮CC⋮CH) (M = Ni (7a), Pd (7c), Pt (7f)) is now complete. When 7c and [(dippe)Pd0] are combined, the dinuclear complex {(dippe)Pd}2(μ-RC⋮CH) (R = C⋮CH (7e)) is formed in solution, whereas isomeric {(dippe)Pd}2{μ-(1,2-η2):(3,4-η2)-HC⋮CC⋮CH} (7d) is present in the solid state. The preparation of the Pd0−1-alkyne complexes refutes the conventional wisdom that this type of compound is inherently unstable. By reaction of (dippe)Pd(C2H4) with internal alkynes C2R2 the complexes (dippe)Pd(RC⋮CR) (R = Me (8a), Ph (9), CO2Me (10), SiMe3 (11)) have also been prepared. Combining 8a with [(dippe)Pd0] affords dinuclear {(dippe)Pd}2(μ-MeC⋮CMe) (8b). Finally, solution thermolysis of 2b and 8b gives rise to dinuclear alkyne-free Pd2(dippe)2 (12).