30376-89-7

Upstream product

• 28966-81-6 trans-bis(triphenylphosphine)palladium dichloride 
• 789-25-3 HSiPh₃ 
• 14221-01-3 tetrakis(triphenylphosphine) palladium⁽⁰⁾ 
• 1118-46-3 Trichlorbutylstannan 
• 63864-53-9 trans-[Pd(Ph)Cl(PPh₃)2] 
• 1333-74-0 hydrogen 
• 13965-03-2 bis-triphenylphosphine-palladium(II) chloride 
• 766-08-5 methylphenylsilane 

Downstream Products

• 62125-38-6 Pd(Cl)2(P(C₆H₅)3)(CNC₆H₃(CH₃)2) 

Relevant academic research and scientific papers

Spontaneous multiple insertion of a bulky aromatic isocyanide into the palladium-hydride bond of trans-[Pd(H)Cl(PPh3)2], leading to formation of heterobicyclic and pyrrole compounds

The reaction of [PdCl2(PPh3)2] (1) with an excess of 2,6-xylyl isocyanide (XylNC) and H2SiMePh in refluxing toluene gave a mononuclear palladium complex of a polyimino ligand, [Pd{C(=NR)C(=NR)C(=NR)C(=NR)CH(=NR)}(C=NR)Cl]· 1/2C6H6 (3·1/2C6H6: R = Xyl, 30%), and a novel heterobicyclic compound, 2,6-(2′,6′-xylyl) 2-3,7-(N-2′,6′-xylylimino) 2-4,8-(N-2′,6′-xylylamino) 2-2,6-diazabicyclo[3.3.0]octa-4,8-diene (4a, 15%), structures of which were determined by X-ray analyses. When the reaction was carried out in the presence of triethylamine, the yield of 4a increased up to 44%. The complex 3 involves a pentaimino moiety [-C(=NR){C(=NR)}3CH(=NR)] derived from a successive insertion of isocyanide into the palladium-hydride bond of trans-[Pd(H)Cl(PPh3)2] (2), which was generated from the reaction of 1 and H2SiMePh in situ. The pentaimino ligand attaches to the metal through the carbon atom of the α-imino group and the lone pair electron of the γ-imino nitrogen atom, resulting in a five-membered chelate ring. The reaction of 3 with XylNC in the presence of H2SiMePh afforded the heterobicyclic compound 4a. Similar treatments of 3 with 2,4,6-mesityl isocyanide (MesNC) and carbon monoxide (～80 kg cm-2) in the presence of H2SiMePh gave 2,6-(2′,6′-xylyl) 2-3-(2′,4′,6′-mesitylimino)-7-(2′,6′- xylylimino)-4,8-(2′,6′-xylylamino) 2-2,6-diazabicyclo[3.3.0]octa-4,8-diene(5)and2,6-(2′,6′- xylyl) 2-7-(2′,6′-xylylimino)-4,8-(2′,6′-xylylamino) 2-2,6-diazabicyclo[3.3.0]octa-4,8-dien-3-one (6), respectively. The structure of 6 was confirmed by X-ray crystallography. When complex 3 was treated with HC=CPh, a pyrrole compound, 1-(2′,6′-xylylamino)-2-phenyl-4-R′-pyrrole (R′ = Ci=NR)-{C(=NR)}2CH(=NR), R = Xyl) (7), was obtained. The structure of 7·C6H6 was confirmed by X-ray crystallography. Possible mechanisms for 4-7 were proposed.

Pd-catalyzed hydroaminocarbonylation of alkynes with aliphatic amines and its mechanism study

This work describes the hydroaminocarbonylation of alkynes with aliphatic amines without the addition of any acid additive. Excellent conversion and regioselectivity toward the formation of branched amides were obtained over a dppp-based Pd-catalytic syst

Oxidative addition of Sn-C bonds on palladium(0): Identification of palladium-stannyl species and a facile synthetic route to diphosphinostannylene- palladium complexes

Methyl-, phenyl-, and n-butyltin trichloride RSnCl3 (R = Me, Ph, nBu) react selectivily with palladium(0)-phosphine precursors through the unprecedented oxidative addition of the Sn-C bond. With [Pd(2-PyPPh2)3] (2-PyPPh2 = 2-pyridyldiphenylphoshine), the reaction cleanly leads to stable cationic dichlorostannylene palladium complexes of the general formula trans-[PdR(SnCl2(2-PyPPh2)2)][X] (X = Cl, R = Me ([5]Cl), R = Ph ([6]Cl), R = nBu ([11]Cl); X = RSnCl4, R = Me ([5][MeSnCl4]), R = Ph ([6][PhSnCl4]), R = nBu ([11][nBuSnCl4])). The SnCl 2(2-PyPPh2)2 fragment, formed by intramolecular coordination of the pyridyl groups to the dichlorostannylene moiety, can be considered as a self-assembled pincer-type ligand with a remarkable ability to suppress β-H elimination in its Pd-alkyl derivatives: [11][ nBuSnCl4], containing a Pd-nBu moiety, was found to be stable up to 70 °C. Oxidative addition of SnCl4 on [Pd(2-PyPPh2)3] resulted in trans-[PdCl(SnCl 2(2-PyPPh2)2)]Cl ([7]Cl) and trans-[PdCl(SnCl3(2-PyPPh2)2)] (8). The molecular structure of 8 was determined by single-crystal X-ray crystallography, indicating that the Sn atom of the trichlorostannyl function has an octahedral coordination geometry. In contrast, oxidative addition of the Sn-C bond of RSnCl3 on [Pd(PPh3)4] resulted in palladium trichlorostannyl complexes that were not stable toward cis-trans isomerization, (partial) elimination of SnCl2 (R = Me, Ph), or β-H elimination (R = nBu). The resulting mixtures of palladium alkyl and palladium hydride species were analyzed by multinuclear NMR, resulting in the identification of novel cis-[PdMe(SnCl3)(PPh3) 2] (cis-4), trans-[PdMe(SnCl3)(PPh3) 2] (trans-4), and cis-[PdH(SnCl3)(PPh3) 2] (cis-10) along with previously observed trans-[PdPh(Cl)(PPh 3)2] (1), trans-[PdMe(Cl)(PPh3)2] (3), trans-[PdH(SnCl3)(PPh3)2] (trans-10), and trans-[PdH(Cl)(PPh3)2] (9).

[Pd(H)(SnCl3)L2]: The key active species in the catalyzed alkoxycarbonylation reaction of terminal alkenes

The four complexes [Pd(H)(Cl)L2] and [Pd(H)(SnCl 3)L2], L = PPh3, PCy3, have been synthesized and fully characterized by multinuclear NMR. They represent the active species of the hydride palladium-catalyzed alkoxycarbonylation of terminal alkenes. Isolation of the model acylplatinum complex, resulting from the carbonylation of dihydromyrcene, clearly shows that SnCl2 as co-catalyst produces a SnCl3 ligand which modulates the metal center electron density.

Hydride route for the palladium-catalysed cyclocarbonylation of monoterpenes

This paper focuses on the mechanism by which a monoterpene undergoes a cyclocarbonylation reaction catalysed by a palladium complex. Evidence is provided, based on intermediate species observed under pressure or with various ligands, that the catalytic cycle follows a hydride route starting from [Pd(H)(SnCl3)L2]. The [Pd(H)(SnCl3)L 2] complexes (L = PPh3 or PCy3) have been observed for the first time by multinuclear NMR spectroscopy. Cationic hydride complexes or palladium(0) precursors show either no or poor reactivity. Studies related to model platinum complex chemistry have detected an acylplatinum species. Most of the observations have been done on the cyclocarbonylation of isopulegol, dihydromyrcenol or isolimonene into the corresponding lactones or cyclopentanones. The use of dihydromyrcene allowed us to observe the acylplatinum complex and the corresponding elusive acylpalladium species. The co-catalytic role of SnCl2 is also demonstrated. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.

Characterisation of Hydridopalladium Complexes

The hydride complex trans- (X = Cl or Br) have been prepared in good yield by hydrogenolysis of trans- or trans-.They have been fully characterised by NMR and IR spectroscopic measurements and shown to have t

Formation of Heterobicyclic Compounds through Successive Insertion of Isocyanides into a Palladium-Hydride Bond

Reaction of PdCl2(PPh3)2 1 with an excess of H2SiMePh and 2,6-xylyl isocyanide gives *1/2C6H6 (3, R = 2,6-xylyl) and heterobicyclic compound 2,6-(2',6'-xylyl)2-3,7-(N-2',6'-xylylimino)2-4,8-(N-2',6'-xylylamino)2-2,6-diaza-bicycloocta-4,8-d