69861-71-8

Usage

Uses

Used in Chemical Synthesis:
Bis[Tris(2-methylphenyl)phosphine]palladium is used as a catalyst for palladium-catalyzed cross-coupling reactions, which are essential in the formation of carbon-carbon bonds. These reactions are widely employed in the synthesis of complex organic molecules, including pharmaceuticals, agrochemicals, and advanced materials.
Used in Pharmaceutical Industry:
In the pharmaceutical industry, Bis[Tris(2-methylphenyl)phosphine]palladium is used as a catalyst for the amination and arylation reactions, which are crucial for the synthesis of various drug molecules. These reactions allow for the introduction of nitrogen-containing functional groups and aromatic rings, respectively, into the molecular structure, enhancing the biological activity and pharmacological properties of the resulting compounds.
Used in Material Science:
In the field of material science, Bis[Tris(2-methylphenyl)phosphine]palladium is utilized as a catalyst for Kumada coupling and Heck coupling reactions. These processes are vital in the synthesis of conjugated polymers and other advanced materials with unique electronic, optical, and mechanical properties. The catalyst plays a significant role in enabling the formation of these materials with high efficiency and selectivity.
Used in Research and Development:
Bis[Tris(2-methylphenyl)phosphine]palladium is also employed in research and development laboratories, where it is used to explore new reaction pathways and develop innovative synthetic methods. Its versatility and efficiency make it an indispensable tool for chemists working on the design and synthesis of novel organic compounds and materials.

Reactions

Catalyst used in the palladium-catalyzed amination of aryl and heteroaryl tosylates at room temperature.

Upstream product

• 6163-58-2 tris-(o-tolyl)phosphine 
• 32005-36-0 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 
• 52409-22-0 tris-(dibenzylideneacetone)dipalladium⁽⁰⁾ 
• 172418-32-5 trans-di(μ-acetato)bis[o-(di-o-tolylphosphino)benzyl]dipalladium(II) 
• 210691-06-8 (μ-η(2),η(2)-C7H12)[Pd(η(2),η(2)-C7H12)]2 
• 40691-33-6 dichlorobis(tri-O-tolylphosphine)palladium 
• 183862-94-4 [Pd(OCOCH₃)(HN(C₂H₅)2)(C₂₁H₂₀P)] 

Downstream Products

• 53199-31-8 bis(tri-t-butylphosphine)palladium⁽⁰⁾ 
• 157106-76-8 [[(CH₃C₆H₄)3P]Pd(C₆H₄C₄H₉)(Br)]2 
• 213540-40-0 ((C₆H₅)3P)2Pd(Br)(CHC(CH₃)2) 
• 176780-03-3 (Pd[P(o-tolyl)3](4-(t)Bu-C6H4)(μ-Br))2 
• 727722-34-1 bromo(4-chlorophenyl)(1,2-bis(diphenylphosphino)benzene)palladium 
• 727722-37-4 bromo(4-(trifluoromethyl)phenyl)(1,2-bis(diphenylphosphino)benzene)palladium 
• 330783-82-9 [Pd(P(o-tolyl)3)(2-Me-5-t-Bu-C6H3)(μ-Br)]2 
• 330980-08-0 [Pd(P(o-tolyl)3)(2-Me-5-t-Bu-C6H3)(μ-I)]2 
• 727722-32-9 bromo(phenyl)(1,2-bis(diphenylphosphino)benzene)palladium 
• 727722-36-3 bromo(4-methoxyphenyl)(1,2-bis(diphenylphosphino)benzene)palladium 
• 727722-33-0 bromo(4-cyanophenyl)(1,2-bis(diphenylphosphino)benzene)palladium 
• 727722-35-2 bromo(3-chlorophenyl)(1,2-bis(diphenylphosphino)benzene)palladium 

Relevant academic research and scientific papers

Capturing a ghost. synthesis and structural characterization of Pd(dba)[P(o -Tol)3]2

In an effort to improve upon a literature synthesis of bis[tris(o-tolyl) phosphine]palladium(0) (1) from tris(o-tolyl)phosphine and Pd 2(dba)3, we instead isolated a new compound which proved to have the composition Pd(dba)[P(o-Tol)3]2 (2), upon analysis by X-ray crystallography. While this is not the first known palladium compound containing both dba and phosphine ligands, it is, to our knowledge, the first containing dba and tris(o-tolyl)phosphine. This is significant, because mixtures of Pd2(dba)3 and tris(o-tolyl)phosphine are routinely used in cross-coupling protocols, and palladium complexes containing dba and tris(o-tolyl)phosphine have been cited as intermediates in organometallic and polymerization reactions. The most interesting crystallographic parameter for 2 is an abnormally long Pd-P bond length of 2.388(1) A, which we believe is the cause of this complex's metastability. We also present an alternative synthesis of 1 that does not require a large excess of phosphine.

Stoichiometric Studies on the Carbonylative Trifluoromethylation of Aryl Pd(II) Complexes using TMSCF3 as the Trifluoromethyl Source

We have performed a series of stoichiometric studies in order to identify viable steps for a hypothetical catalytic cycle for the palladium-mediated carbonylative coupling of an aryl bromide with TMSCF3. Our work revealed that benzoyl Pd(II) complexes bearing Xantphos or tBu3P as the phosphine ligands, which are generated from the corresponding PdII(Ph)Br complexes exposed to stoichiometric 13CO from 13COgen, were unable to undergo transmetalation and reductive elimination to trifluoroacetophenone. Instead, in the presence of base and additional CO, these organometallic complexes readily underwent reductive elimination to the acid fluoride. Attempts to determine whether the acid fluoride could represent an intermediate for acetophenone production were unrewarding. Only in the presence of a boronic ester did we observe some formation of the desired product, although the efficiency of transformation was still low. Finally, we investigated the reactivity of four phosphine-ligated PdII(Ph)CF3 complexes (Xantphos, DtBPF, tBu3P, and triphenylphosphine) with carbon monoxide. With the exception of the tBu3P-ligated complex, all other metal complexes led to the facile formation of trifluoroacetophenone. We also determined in the case of triphenylphosphine that CO insertion occurred into the Pd-Ar bond, as trapping of this complex with n-hexylamine led to the formation of n-hexylbenzamide.

Stoichiometric and Catalytic Aryl-Perfluoroalkyl Coupling at Tri-tert-butylphosphine Palladium(II) Complexes

This Communication describes studies of Ph-RF (RF = CF3 or CF2CF3) coupling at Pd complexes of general structure (PtBu3)PdII(Ph)(RF). The CF3 analogue participates in fast Ph-CF3 coupling (II complex. Furthermore, they show that this undesired pathway can be circumvented by changing from a CF3 to a CF2CF3 ligand. Ultimately, the insights gained from stoichiometric studies enabled the identification of Pd(PtBu3)2 as a catalyst for the Pd-catalyzed cross-coupling of aryl bromides with TMSCF2CF3 to afford pentafluoroethylated arenes.

METAL COMPOUND AND PREPARATION METHOD THEREFOR

The invention concerns the preparation of a metal chelate, in particular a precious metal β-diketonate or a precious metal phosphine complex MLaXb, where M is a metal atom, L is a ligand, X is an anion which is preferably a halide, HCO3ˉ, NO3ˉ, CO32é or carboxylate, a is a number equal to or less than the coordination number of the metal, b is 0, 1, 2 or 3, comprising reacting an ammine compound of metal M with a complexing compound, which is preferably a phosphine or a diketonate. Metal compounds which can be made by this process are also described.

1,6-Diene complexes of palladium(0) and platinum(0): Highly reactive sources for the naked metals and [L-M0] fragments

The complexes (cod)MCl2 (M = Pd, Pt; cod = cis,cis-1,5-cyclooctadiene) react with Li2(cot) (cot = cyclooctatetraene) in a 1,6-diene/diethyl ether mixture (1,6-diene = hepta-1,6-diene, diallyl ether, dvds (1,3-divinyl- 1,1,3,3-tetramethyldisiloxane)) to afford the isolated homoleptic dinuclear Pd0 and Pt0 compounds Pd2(C7H12)3 (1), Pd2(C6H10O)3·C6H10O (2'; 2: Pd2(C6H10O)3), Pd2(dvds)3 (3), and Pt2(C7H12)3 (4). When 1-4 are treated with additional 1,6-diene the equally homoleptic but mononuclear derivatives of type M(1,6-diene)2 (5-8) and with ethene the mixed alkene complexes (C2H4)M(1,6-diene) (9-12) are obtained in solution. Complexes 1-12 react with donor ligands such as phosphanes, phosphites, or (t)BuNC to give isolated complexes of types L-M(1,6-diene) (13-41), which have also been prepared by other routes. In all complexes the metal centers are TP-3 coordinated: complexes 1-4 contain chelating and bridging 1,6-diene ligands, whereas the other complexes contain a chelating 1,6-diene ligand and an η2-alkene (5-12) or η1-donor ligand (13-41). Of the studied 1,6-diene complexes the hepta-1,6-diene derivatives are most reactive, while the diallyl ether complexes are often more convenient to handle. The readily isolable dinuclear hepta-1,6-diene and diallyl ether complexes 1, 2', and 4, and their mononuclear pure olefin derivatives are among the most reactive sources for naked Pd0 and Pt0. The corresponding L-M(1,6-diene) complexes are equally reactive precursor compounds for the generation of [L-M0] fragments in solution, which for M =Pd are available otherwise only with difficulty. The results are significant for the operation of naked Pd0 and L-Pd0 catalysts in homogeneous catalysis.

Phosphapalladacycle-catalyzed heck reactions for efficient synthesis of trisubstituted olefins: Evidence for palladium(0) intermediates

The coupling reaction of 1,1-disubstituted olefins (α-methyl-styrene, n-butyl methacrylate) with various aryl bromides (Heck reaction) has been studied as a new concept to synthesize trisubstituted olefins. Surprisingly, the nature of the base dramatically influences the product distribution. Thus, a systematic investigation on the role of base in Heck reactions of 1,1-disubstituted olefins was performed. Less coordinating bases like NaOAc, NaOBz or Na2CO3 yield a statistical distribution of regioisomers with the terminal olefin 10 as the major product. However, by using amines like Bu3N or diisopropylethylamine (DIPEA) as base internal olefins can be synthesized with high selectivities. With phosphapalladacycle 3 as catalyst precursor, we were able to obtain catalyst turnover numbers up to 1000, while Pd(OAc)2/2PPh3 was one order of magnitude less active. Analysis of the reaction profile by kinetic investigations led to the postulation of a reduction and subsequent oxidative addition of the catalyst precursor 3 to form 12 as catalytically active intermediate.

A route to Pd0 from Pd(II) metallacycles in amination and cross- coupling chemistry

Pd(II)/Pd(IV) or Pd(II)/Pd0? The unusual Pd(II) catalyst 1 was reduced to a Pd0 complex by reaction with an amine and a base. β-Hydrogen elimination and subsequent C-H bond-forming reductive elimination generate a coordinate tris(o-tolyl) phosphane. The same palladium(II) metallacycle was reduced to Pd0 in a cross-coupling reaction by C-C bond-forming reductive elimination to form coordinated P(oTol)2-(C6H4CH2Ar). Thus, these compounds can react by a Pd(II)/Pd0-containing catalytic cycle.

Structural characterization and simple synthesis of {Pd[P(o-Tol)3]2}, dimeric palladium(II) complexes obtained by oxidative addition of aryl bromides, and corresponding monometallic amine complexes

The palladium(0) complex {Pd[P(o-Tol)3]2} was prepared by addition of P(o-Tol)3 to crude "[Pd(DBA)2]", which is an approximately equimolar mixture of Pd2(DBA)3 and Pd(DBA)3, followed by crystallization from the reaction medium by addition of ether. The formation of {Pd[P(o-Tol)3]2} appeared to be driven by its insolubility in the benzene/ether solvent mixture. Benzene solutions of "[Pd(DBA)2]" and P(o-Tol)3 did not contain amounts of the L2Pd compound that could be detected by 31P NMR spectroscopy. {Pd[P(o-Tol)3]2} was characterized crystallographically and showed an exactly linear geometry. Similar Pd(O) compounds {Pd[P(2,4-dimethylphenyl)3]2}, {Pd[P(2-methyl-4-fluorophenyl)3]2}, and the low-coordinate trialkylphosphine complex {Pd[P(t-Bu)a]2} were also prepared by this method, but [Pd(PCy3)2-(DBA)] was produced from reactions involving PCy3 and "[Pd(DBA)2]", and [Pd(TMPP)(DBA)2] was isolated after addition of tris(1,3,5-trimethoxyphenyl)phosphine (TMPP) to "[Pd(DBA)2]". The oxidative addition of aryl halides to {Pd[P(o-Tol)3]2} at room temperature led to dimeric products {Pd[P(o-Tol)3](Ar)(Br)}2. An example of these compounds was characterized crystallographically as well as by solution molecular weight analysis. This aryl halide complex was shown to be dimeric in the solid state as well as in solution. The NMR spectra of the large triarylphosphine complexes showed temperature dependent behavior, presumably due to isomerizations and ligand rotations that occurred on the NMR time scale. The aryl halide compounds did not form four-coordinate monometallic species in the presence of excess P(o-Tol)3, but they did undergo cleavage to four-coordinate monometallic complexes upon addition of primary and secondary amines.