51209-78-0Relevant articles and documents
Sterically hindered (pyridyl)benzamidine palladium(II) complexes: Syntheses, structural studies, and applications as catalysts in the methoxycarbonylation of olefins
Akiri, Saphan O.,Ojwach, Stephen O.
, (2021/09/09)
Reactions of ligands (E)-N′-(2,6-diisopropylphenyl)-N-(4-methylpyridin-2-yl)benzimidamide (L1), (E)-N′-(2,6-diisopropylphenyl)-N-(6-methylpyridin-2-yl)benzimidamide (L2), (E)-N′-(2,6-dimethylphenyl)-N-(6-methylpyridin-2-yl)benzimidamide (L3), (E)-N′-(2,6-dimethylphenyl)-N-(4-methylpyridin-2-yl)benzimidamide (L4), and (E)-N-(6-methylpyridin-2-yl)-N′-phenylbenzimidamide (L5) with [Pd(NCMe)2Cl2] furnished the corresponding palladium(II) precatalysts (Pd1–Pd5), in good yields. Molecular structures of Pd2 and Pd3 revealed that the ligands coordinate in a N^N bidentate mode to afford square planar compounds. Activation of the palladium(II) complexes with para-tolyl sulfonic acid (PTSA) afforded active catalysts in the methoxycarbonylation of a number of alkene. The resultant catalytic activities were controlled by the both the complex structure and alkene substrate. While aliphatic substrates favored the formation of linear esters (>70%), styrene substrate resulted in the formation of predominantly branched esters of up to 91%.
Methoxycarbonylation of olefins catalysed by homogeneous palladium(II) complexes of (phenoxy)imine ligands bearing alkoxy silane groups
Akiri, Saphan O.,Ojwach, Stephen O.
, p. 236 - 243 (2019/03/02)
The Schiff base compounds 2-phenyl-2-((3(triethoxysilyl)propyl)imino)ethanol (HL1) and 4-methyl-2-((3(triethoxysilyl)propyl)imino)methyl)phenol (HL2) were synthesized via condensation reactions of a suitable ketone or aldehyde and (3-aminopropyl) triethoxy silane (APTES). Whereas the reactions of HL1 and HL2 with [Pd(OAc)2] afforded the bis(chelated) palladium compounds [Pd(L1)2] (1) and [Pd(L2)2] (2), treatments of HL1 and HL2 with [Pd(NCMe)2Cl2] gave the mono(chelated) complexes [Pd(HL1)2Cl2] (3) and [Pd(HL2)2Cl2] (4) respectively. Structural characterization of the compounds was achieved using NMR and FT-IR spectroscopies, mass spectrometry and micro-analyses. Complexes 1–4 gave active catalysts in the methoxycarbonylation of higher olefins producing linear esters as the major products. The coordination environment around the palladium center of the complexes dictated the relative catalytic activity, where the bis(chelated) analogues 1 and 2 were more active than the mono(chelated) analogues 3 and 4. The nature of the acid promoter, phosphine groups, solvent system, olefin substrate and reactions conditions influenced the catalytic behaviour of the complexes.
Palladium(II) complexes bearing mixed N^N^X (X?=?O and S) tridentate ligands as pre-catalysts for the methoxycarbonylation of selected 1-alkenes
Kumar, Kamlesh,Darkwa, James
, p. 249 - 257 (2017/10/27)
The methoxycarbonylation of selected 1-alkenes catalyzed by various neutral and cationic palladium(II) complexes, containing mixed N^N^X (X = O and S) tridentate ligands 2-[(3,5-dimethyl-1H-pyrazol-1-yl)methyl]-6-(phenoxymethyl)pyridine (L1), 2-[(3,5-di-tert-butyl-1H-pyrazol-1-yl)methyl]-6-(phenoxymethyl)pyridine (L2), 2-[(3,5-dimethyl-1H-pyrazol-1-yl)methyl]-6-(phenylthiomethyl)pyridine (L3), 2-[(3,5-di-tert-butyl-1H-pyrazol-1-yl)methyl]-6-(phenylthiomethyl)pyridine (L4), has been investigated. Neutral complexes, [(?2-L1)Pd(CH3)(Cl)] (1a), [(?2-L2)Pd(CH3)(Cl)] (2a), [(?2-L3)Pd(CH3)(Cl)] (3a), [(?2-L4)Pd(CH3)(Cl)] (4a), and the salts, [(?3-L3)Pd(CH3)][BAr4F] (3c) and [(?3-L4)Pd(CH3)][BAr4F] (4c), underwent complete decomposition during the reaction to palladium black and showed no catalytic activity. However, the addition of PPh3 to the reaction dramatically increased the catalytic activity. On the other hand, the salts, [(?2-L1)Pd(CH3)(PPh3)][BAr4F] (1b), [(?2-L2)Pd(CH3)(PPh3)][BAr4F] (2b), [(?2-L3)Pd(CH3)(PPh3)][BAr4F] (3b) and [(?2-L4)Pd(CH3)(PPh3)][BAr4F] (4b), showed good conversion of the selected olefins to branched and linear esters without PPh3. Addition of PPh3 to reactions with 1b-4b significantly improved catalytic activity. All decomposition of complexes led to the formation of the known palladium complexes, [Pd(PPh3)2(Cl)(CH3)] and [Pd(PPh3)2Cl2]. The decomposition of all palladium complexes could be followed by NMR studies and [Pd(PPh3)2Cl2] could be isolated from the crude methoxycarbonylation reaction.