Aminophosphine-palladium(II) complexes: Synthsesis, structure and applications in Suzuki and Heck cross-coupling reactions

ŞAHİN, Ertan
Gumgum, Bahattin
Özkar, Saim
Reaction of furfurylamine with 1 or 2 equivalents of PPh2Cl in the presence of Et3N, proceeds under anaerobic conditions in thf to give furfuryl-2-(N-diphenylphosphino)amine, Ph2PNHCH2-C4H3O, 1 and furfuryl-2-(N,N-bis(diphenylphosphino)amine), (Ph2P)(2)NCH2-C4H3O, 2, respectively. The reactions of 1 and 2 with MCl2(cod) (M = Pd, Pt; cod = 1,5-cyclooctadiene) or Pt(CH3)(2)(cod) yield complexes [M(Ph2PNHCH2-C4H3O)(2)Cl-2] (M= Pd 1a, Pt 1b), [Pt(Ph2PNHCH2-C4H3O)(2)(CH3)(2)] (1c), and [M((Ph2P)(2) NCH2-C4H3O)Cl-2] (M= Pd 2a, Pt 2b), [Pt((Ph2P)(2)NCH2-C4H3O)(CH3)(2)] (2c), respectively. All the compounds were isolated as analytically pure substances and characterized by NMR, IR spectroscopy and elemental analysis. Representative solid-state structures of 2a and 2b were also determined by X-ray single crystal diffraction technique. Furthermore, the palladium complexes 1a and 2a were tested and found to be highly active catalysts in the Suzuki coupling and Heck reaction affording biphenyls and trans-stilbenes, respectively.


Carbonyltungsten(0) complexes of acryloylferrocene: Synthesis and characterization
Boga, Dilek Ayse; Özkar, Saim (Elsevier BV, 2006-07-15)
Photolysis of hexacarbonyltungsten(0) in the presence of acryloylferrocene in n-hexane solution at 10 C yields pentacarbonyl(eta(2)-acryloylferrocene)tungsten(0) (1) as the only photo-substitution product, different from the general reaction pattern observed for the Group 6 metal carbonyls with other olefins. W(CO)5(eta(2)-acryloylferrocene) (1) decomposes in solution to the parent hexacarbonyltungsten(0) and free acryloylferrocene. Trimethylphosphite was introduced as ligand into the molecule to increase t...
Benzaldehyde lyase-catalyzed enantioselective carboligation of aromatic aldehydes with mono- and dimethoxy acetaldehyde
Demir, Ayhan Sıtkı; Sesenoglu, O; Dunkelmann, P; Muller, M (American Chemical Society (ACS), 2003-06-12)
Benzaldehyde lyase from the Pseudomonas fluorescens catalyzes the reaction of aromatic aldehydes with methoxy and dimethoxy acetaldehyde and furnishes (R)-2-hydroxy-3-methoxy-1-arylpropan-1-one and (R)-2-hydroxy-3,3-dimethoxy-1-arylpropan-1-one in high yields and enantiomeric excess via acyloin linkage. Aromatic aldehydes and benzoins are converted into enamine-carbanion-like intermediates prior to carboligation.
Amination/annulation of chlorobutenones with chiral amine compounds: synthesis of 1,2,4-trisubstituted pyrroles
Demir, Ayhan Sıtkı; Igdir, AC; Gunay, NB (Elsevier BV, 2005-10-03)
A series of 1,2,4-trisubstituted pyrroles have been synthesized in 83-96% yields on treatment of chiral primary amines, amino alcohols and esters of alpha-amino acids with different chlorobutenones in benzene-triethylamine. The conversions proceed without racemization.
Axial water substitution kinetics of sulphato- and hydrogenphosphato-bridged binuclear platinum(III) complexes
Camadanli, S; Deveci, N; Gokagac, G; Isci, H (Elsevier BV, 2003-07-22)
The kinetics of the axial water substitution reactions for [Pt-2(B-B)(4)(H2O)(2)](2-) (B-B = SO42-, HpO(4)(2-)) with Cl-, Br- and SCN- are reported in acidic aqueous solution. With a large excess of entering ligand and hydrogen ion, only the disubstituted product complex was formed. The reaction rates are first order with respect to the substrate complex and entering ligand and decrease with increasing H+ concentration. In the presence of 0.10 M H+, the rate constants for the replacement of the first water ...
Electrochemistry of nickel(II) complexes with N,N'-bis(3,5-di-tert-butylsalicylidene)polymethylenediamines
Ozalp-Yaman, S; Kasumov, VT; Önal, Ahmet Muhtar (Elsevier BV, 2005-10-03)
The electrochemical oxidation of several N,N'-polymethylenebis(3,5-di-tert- butylsalicylaldiminato)nickel(II) complexes, Ni(L-x), has been studied by cyclic voltammetry and in situ UV-Vis spectroscopy in DMF Cyclic voltammograms of Ni(L-x) (x = 1-4) complexes displayed two-step oxidation processes under nitrogen gas atmosphere. The first oxidation peak potentials of all the Ni(II) complexes corresponds to the reversible one-electron oxidation process of the metal center, yielding Ni(III) species. EPR spectr...
Citation Formats
M. AYDEMİR, A. BAYSAL, E. ŞAHİN, B. Gumgum, and S. Özkar, “Aminophosphine-palladium(II) complexes: Synthsesis, structure and applications in Suzuki and Heck cross-coupling reactions,” INORGANICA CHIMICA ACTA, pp. 10–18, 2011, Accessed: 00, 2020. [Online]. Available: