Abstract
In a refluxing chloroform solution, the η1-pyrimidinyl {pyrimidinyl = C4H3N2} palladium complex [Pd(PPh3)2(η1-C4H3N2)(Br)], 1 exhibited intermolecular displacement of two triphenylphosphine ligands to form the doubly bridged η2-pyrimidinyl Dipalladium complex [Pd(PPh3)(Br)]2(μ,η2-C4H3N2)2, 3. The treatment of 1 with Hdppa {Hdppa = N,N-bisdiphenyl phosphinoamine} in refluxing dichloromethane yielded the doubly bridged Hdppa dipalladium complex [Pd(Br)]2(μ,η2-Hdppa)2, 4. Complex 1 reacted with the bidentate ligand, NH4S2CNC4H8 and, NaS2COEt, and the tridentate ligand, KTp {Tp = tris(pyrazoyl-1-yl)borate}, to form the η2-dithio η1-pyrimidinyl complex [Pd(PPh3)(η1-C4H3N2)(η2-SS)], (5: SS = S2CNC4H8; 6: SS = S2COEt) and η2-Tp η1-pyrimidinyl complex [Pd(PPh3)(η1-C4H3N2)(η2-Tp)], 7, respectively. Treatment of 1 with AgBF4 in acetonitrile at room temperature resulted in the formation of the doubly bridged η2-pyrimidinyl dipalladium complex [{Pd(PPh3)(CH3CN)}2(μ,η2-C4H3N2)2][BF4]2, 8. All of the complexes were identified using spectroscopic methods, and complexes 3, 4, and 8 were determined using single-crystal X-ray diffraction analyses.
Highlights
C-F activation of a pyrimidine at nickel was reported by Braun [1]
The catalytic activity of dipalladium for Suzuki-Miyaura cross-coupling reactions [1], various organoboronic acids, and aryl bromides by the pyridyl-bridged palladium complex [2] for Suzuki cross-coupling reactions, coupling of aryl boronic acids and aryl halides by the palladacycle [3] complex, the imidazolium palladium complex [4] for Heck reactions, and intramolecular reductive elimination by a Pd-N binuclear complex [5] are crucial in the organic synthesis [6] of palladium complexes catalyzed for forming a Molecules 2020, 25, 2035; doi:10.3390/molecules25092035
To obtain better understanding of how these ligands interact withapplication the metal center, thepyrimidinyl synthesis of synthesis of adoubly bridged dipalladium complexes, and the of the doubly bridged dipalladium and the application thesyntheses pyrimidinyl dipalladium complexes dipalladium complexes in complexes, organic synthesis, we report of the and crystal structures of in organic synthesis, we report the syntheses and crystal structures of dipalladium complexes, including dipalladium complexes, including the 1, 3-pyrimidinyl containing ligand
Summary
C-F activation of a pyrimidine at nickel was reported by Braun [1]. The catalytic activity of dipalladium for Suzuki-Miyaura cross-coupling reactions [1], various organoboronic acids, and aryl bromides by the pyridyl-bridged palladium complex [2] for Suzuki cross-coupling reactions, coupling of aryl boronic acids and aryl halides by the palladacycle [3] complex, the imidazolium palladium complex [4] for Heck reactions, and intramolecular reductive elimination by a Pd-N binuclear complex [5] are crucial in the organic synthesis [6] of palladium complexes catalyzed for forming a C-C bond.Molecules 2020, 25, 2035; doi:10.3390/molecules25092035 www.mdpi.com/journal/molecules Molecules of 13 22 ofWe recently reported syntheses, reactivities, inter- and intramolecular dissociation, and crystalWe recently syntheses, reactivities, inter- and intramolecular dissociation, and[9], crystal structures of Pd reported complexes containing thiocarbarmoyl [7], oxythiocarbonyl [8], thiazolinyl and structures ofPd complexes containing thiocarbarmoyl [8], thiazolinyl [9], and methylpyridinyl [10] moieties. Reactivities, inter- and intramolecular dissociation, and crystal. Reactivities, inter- and intramolecular dissociation, and[9], crystal structures of Pd reported complexes containing thiocarbarmoyl [7], oxythiocarbonyl [8], thiazolinyl and structures of. Pd complexes containing thiocarbarmoyl [8], thiazolinyl [9], and methylpyridinyl [10] moieties These ligands induced the formation of binuclear complexes that methylpyridinyl moieties.orThese the formation of binuclear complexes were assisted by [10]. Thetriphenylphosphine sulfur atom of the thiocarbamoyl assists or thesulfur displacement of either the chloride or the thiocarbamoyl ligand assists the displacement of either the chloride or thethe triphenylphosphine ligand ligand to form η2-thiocarbamoyl palladium complexes [11] and thiocarbamoyl-assisted to form η -thiocarbamoyl palladium complexes [11]complexes and the thiocarbamoyl-assisted formation of formation of α−form paddlewheel type dipalladium [12]
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