NMR study on the coordination of dibenzylideneacetone to chiral palladium(0) units. Fluxional behaviour including an intramolecular double bond exchange†

Jalón, Félix A.; Manzano, Blanca R.; Torre, Felipe Gómez-de la; López-Agenjo, Ana; Rodrı́guez, Ana; Weissensteiner, Walter; Sturm, Thomas; Mahı́a, José; Maestro, Miguel A.

doi:10.1039/b101912k

Cited by 34 publications

(22 citation statements)

References 39 publications

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“…Based on these observations, we have tentatively identified this new species as a monophosphine palladium(0)(dba) complex, (1)Pd(dba) n (8). Although we cannot confirm coordination of dba by spectroscopic means, the trans-dibenzylideneacetone ligand provides an asymmetric coordination environment that is typically fluxional at room temperature [41,42]. L 2 Pd(dba) (L = tertiary phosphine) complexes have been previously reported [36,[43][44][45][46][47], but LPd(dba) n complexes of monodentate phosphines have not previously been reported to our knowledge.…”

Section: Discussionmentioning

confidence: 73%

Di-t-butyl(ferrocenylmethyl)phosphine: air-stability, structural characterization, coordination chemistry, and application to palladium-catalyzed cross-coupling reactions

Sliger¹,

Broker²,

Griffin³

et al. 2005

Journal of Organometallic Chemistry

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Section: Discussionmentioning

confidence: 73%

Di-t-butyl(ferrocenylmethyl)phosphine: air-stability, structural characterization, coordination chemistry, and application to palladium-catalyzed cross-coupling reactions

Sliger¹,

Broker²,

Griffin³

et al. 2005

Journal of Organometallic Chemistry

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“…Related complexes, [Pd 0 2 (dba‐Z) 3 ] and [Pd 0 (dba‐Z) 2 ] (dba‐Z=dibenzylidene acetone with different Z‐substituents), have been reported 8. In these complexes, intramolecular dba‐H olefin–olefin exchange occurs readily at Pd 0 , through CO coordination, with several conformers being accessible 9. Addition of ligands (L) such as phosphines (monodentate or bidentate) or bipyridyls10 give complexes of the type [Pd 0 (η 2 ‐dba)(L) 2 ].…”

Section: Introductionmentioning

confidence: 99%

A Remarkable cis‐ and trans‐Spanning Dibenzylidene Acetone Diphosphine Chelating Ligand (dbaphos)

Jarvis

Sehnal

Bajwa

et al. 2013

Chemistry A European J

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A multidentate and flexible diolefin-diphosphine ligand, based on the dibenzylidene acetone core, namely dbaphos (1), is reported herein. The ligand adopts an array of different geometries at Pt, Pd and Rh. At Pt(II) the dbaphos ligand forms cis- and trans-diphosphine complexes and can be defined as a wide-angle spanning ligand. (1)H NMR spectroscopic analysis shows that the β-hydrogen of one olefin moiety interacts with the Pt(II) centre (an anagostic interaction), which is supported by DFT calculations. At Pd(0) and Rh(I), the dbaphos ligand exhibits both olefin and phosphine interactions with the metal centres. The Pd(0) complex of dbaphos is dinuclear, with bridging diphosphines. The complex exhibits the coordination of one olefin moiety, which is in dynamic exchange (intramolecular) with the other "free" olefin. The Pd(0) complex of dbaphos reacts with iodobenzene to afford trans-[Pd(II)(dbaphos)I(Ph)]. In the case of Rh(I), dbaphos coordinates to form a structure in which the phosphine and olefin moieties occupy both axial and equatorial sites, which stands in contrast to a related bidentate olefin, phosphine ligand ("Lei" ligand), in which the olefins occupy the equatorial sites and phosphines the axial sites, exclusively.

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“…This is the earliest and most frequently proposed mechanism [30,42,43,[46][47][48]; (2) olefin-metal dissociation followed by recombination [30]; (3) intermolecular associative process with free alkene, via (4) metal-L or metal-L 0 bond dissociation followed by rotation of the ancillary ligand and recombination (olefin pseudorotation) [42,43]; (5) intermolecular exchange with the free ancillary ligand L-L 0 . In this case, a mechanism has been proposed which involves an olefin-metal dissociation step [30].…”

Section: Fluxional Rearrangementsmentioning

confidence: 99%

Synthesis, stability and reactivity of palladium(0) olefin complexes bearing labile or hemi-labile ancillary ligands and electron-poor olefins

Canovese

Visentin

2010

Inorganica Chimica Acta

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a b s t r a c tAn overview of the general features of electron-poor olefin stabilized palladium(0) complexes bearing labile and hemi-labile ancillary ligands is presented. In particular, we have summarized the synthetic methodologies, the ligands commonly used, and the characterization of such complexes. The behavior of these species in solution is also described with particular attention to their fluxional rearrangements and reactivity. Thus, olefin exchange reactions are described and a comprehensive order of coordinative capability of the most widely used electron-poor alkenes is presented. The reactions of the title complexes dealing with olefin isomerization, oxidative addition, and formation of palladacyclopentadiene derivatives are eventually reported together with their main structural characteristics.

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NMR study on the coordination of dibenzylideneacetone to chiral palladium(0) units. Fluxional behaviour including an intramolecular double bond exchange†

Cited by 34 publications

References 39 publications

Di-t-butyl(ferrocenylmethyl)phosphine: air-stability, structural characterization, coordination chemistry, and application to palladium-catalyzed cross-coupling reactions

Di-t-butyl(ferrocenylmethyl)phosphine: air-stability, structural characterization, coordination chemistry, and application to palladium-catalyzed cross-coupling reactions

A Remarkable cis‐ and trans‐Spanning Dibenzylidene Acetone Diphosphine Chelating Ligand (dbaphos)

Synthesis, stability and reactivity of palladium(0) olefin complexes bearing labile or hemi-labile ancillary ligands and electron-poor olefins

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