185812-86-6Relevant articles and documents
Synthesis and Structural Characterisation of : A Tetrahedral Palladium Cluster with a μ3-Methylidyne Ligand
Burrows, Andrew D.,Mingos, D. Michael P.,Menzer, Stephan,Vilar, Ramon,Williams, David J.
, p. 2107 - 2108 (1995)
The compound has been synthesised from (dba = dibenzylideneacetone), P(t-Bu)3 and CHCl3 and characterised spectroscopically and by single-crystal X-ray analysis; it undergoes substitution reactions with Br(1-) and tertiary phosphines and is a catalyst for the polymerisation of ethyne.
Synthesis and structural characterisation of [Pd2(μ-Br)2(PBut3)2], an example of a palladium(I)-palladium(I) dimer
Vilar, Ramon,Mingos, D. Michael P.,Cardin, Christine J.
, p. 4313 - 4314 (1996)
The syntheses, spectroscopic characterisation and in one case (X = Br) the single-crystal structure of the novel PdI-PdI dimers [Pd2(μ-X)2(PBut3)2] (X = Br or I) have been determined; preliminary results on their reactions with CO, H2, CNC6H3Me2 and C2H2 have also been obtained.
PROCESS
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, (2018/05/16)
The present invention provides a process for the preparation of a complex of formula (I): comprising the step of reacting Pd(diolefin)X2 or PdX2 and PR1 R2R3 in a solvent to form the complex of formula (I), wherein the process is carried out in the absence of a base, the molar ratio of Pd(diolefin)X2 : PR1 R2R3 or PdX2 : PR1 R2R3 is greater than 1 : 1.1, up to about 1 :2.5; each X is independently a halide; and R1, R2 and R3 are independently selected from the group consisting of tert-butyl and isopropyl.
Understanding the Unusual Reduction Mechanism of Pd(II) to Pd(I): Uncovering Hidden Species and Implications in Catalytic Cross-Coupling Reactions
Johansson Seechurn, Carin C. C.,Sperger, Theresa,Scrase, Thomas G.,Schoenebeck, Franziska,Colacot, Thomas J.
supporting information, p. 5194 - 5200 (2017/05/04)
The reduction of Pd(II) intermediates to Pd(0) is a key elementary step in a vast number of Pd-catalyzed processes, ranging from cross-coupling, C-H activation, to Wacker chemistry. For one of the most powerful new generation phosphine ligands, PtBu3, oxidation state Pd(I), and not Pd(0), is generated upon reduction from Pd(II). The mechanism of the reduction of Pd(II) to Pd(I) has been investigated by means of experimental and computational studies for the formation of the highly active precatalyst {Pd(μ-Br)(PtBu3)}2. The formation of dinuclear Pd(I), as opposed to the Pd(0) complex, (tBu3P)2Pd was shown to depend on the stoichiometry of Pd to phosphine ligand, the order of addition of the reagents, and, most importantly, the nature of the palladium precursor and the choice of the phosphine ligand utilized. In addition, through experiments on gram scale in palladium, mechanistically important additional Pd- and phosphine-containing species were detected. An ionic Pd(II)Br3 dimer side product was isolated, characterized, and identified as the crucial driving force in the mechanism of formation of the Pd(I) bromide dimer. The potential impact of the presence of these side species for in situ formed Pd complexes in catalysis was investigated in Buchwald-Hartwig, α-arylation, and Suzuki-Miyaura reactions. The use of preformed and isolated Pd(I) bromide dimer as a precatalyst provided superior results, in terms of catalytic activity, in comparison to catalysts generated in situ.
