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Journal Article

(R2PC2H4PR2)Pd0−1-Alkyne Complexes

MPS-Authors

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

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

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

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

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

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

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Citation

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.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0024-4C65-1
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).