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  (R2PC2H4PR2)Pd0−1-Alkyne Complexes

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.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-0024-4C65-1 Version Permalink: http://hdl.handle.net/11858/00-001M-0000-0024-4C66-0
Genre: Journal Article

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 Creators:
Schager, Frank1, Author
Bonrath, Werner1, Author
Pörschke, Klaus-Richard2, Author              
Kessler, Magnus1, Author
Krüger, Carl3, Author              
Seevogel, Klaus1, Author
Affiliations:
1Max-Planck-Institut für Kohlenforschung, Max Planck Society, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, DE, ou_1445580              
2Research Group Pörschke, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445616              
3Service Department Krüger (XRAY), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445624              

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Free keywords: CATALYZED STANNOLE SYNTHESIS; ACETYLENE COMPLEXES; BUTADIENE COMPLEXES; PALLADIUM COMPLEX; NICKEL(0); PLATINUM; 1,3-DIENES; REACTIVITY; ALKYNES; OLEFIN
 Abstract: 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).

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Language(s): eng - English
 Dates: 1997-03-111997-09-301997-09-30
 Publication Status: Published in print
 Pages: 11
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/om9702035
 Degree: -

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Title: Organometallics
  Other : Organometallics
Source Genre: Journal
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Publ. Info: Washington, USA : American Chemical Society
Pages: - Volume / Issue: 16 (20) Sequence Number: - Start / End Page: 4276 - 4286 Identifier: ISSN: 0276-7333
CoNE: https://pure.mpg.de/cone/journals/resource/954925505259