Synthesis of heterodinuclear hydride complexes by oxidative addition of a transition-metal hydride to Pt(0) and Pd(0) complexes

Komine, Nobuyuki; Kuramoto, Ayako; Yasuda, Toshiyuki; Kawabata, T.; Hirano, Masafumi; Komiya, Sanshiro

doi:10.1016/j.jorganchem.2015.04.048

Cited by 2 publications

(3 citation statements)

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“…In complex B , the Pd and W centers are bridged by the hydride and one of the carbonyl ligands. A similar bridged structure is also suggested in (dppe)Pd(μ-H)(μ-CO)WCp(CO) 2 . The syn insertion of alkenes into the palladium–hydrogen bond in B proceeds to give the trans -(alkyl)(tungsten)palladium(II) intermediate C (step 3).…”

Section: Resultsmentioning

confidence: 71%

“…This isomerization reaction was probably caused by a hydridopalladium species, and we previously reported the formation of the dinuclear hydridopalladium complex by the reaction of the hydride complex with the zerovalent palladium complex. 14 Therefore, the present result suggests prior formation of a dinuclear hydridopalladium−tungsten complex, followed by insertion of dimethyl maleate into the hydrogen− palladium bond and subsequent β-hydride elimination/ reductive elimination of the resulting alkylpalladium complex.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…A similar bridged structure is also suggested in (dppe)Pd(μ-H)(μ-CO)-WCp(CO) 2 . 14 The syn insertion of alkenes into the palladium− hydrogen bond in B proceeds to give the trans-(alkyl)(tungsten)palladium(II) intermediate C (step 3). The trans-(alkyl)(tungsten)palladium(II) intermediate C then isomerizes to the corresponding cis complex D (step 4), and then the C−W reductive elimination from Pd forms an alkyltungsten complex, where the Pd fragment still remains attached with two bridging carbonyl groups (E) (step 5).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Selective Alkene Insertion into Inert Hydrogen–Metal Bonds Catalyzed by Mono(phosphorus ligand)palladium(0) Complexes

et al. 2017

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Isolated mono(phosphorus ligand)palladium(0) complexes catalyzed alkene insertions into hydrogen−tungsten bonds. These insertions using WHCp(CO) 3 with ethyl acrylate and dimethyl fumarate smoothly gave the corresponding alkyltungsten complexes. Kinetic studies involving the stoichiometric reactions and DFT calculations suggest the following steps: (i) formation of a mono(phosphorus ligand)mono(alkene)palladium(0) species, (ii) subsequent reaction of a metal hydride with the palladium(0), (iii) insertion of the coordinated alkene into the resulting palladium hydride, and (iv) reductive elimination between the alkyl and metal on the palladium center to release the alkylmetal species with regeneration of a palladium(0) by a reaction with alkene.

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Section: Resultsmentioning

confidence: 71%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

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