Organometallic ruthenium, rhodium and iridium complexes containing a P-bound thiophene-2-(N-diphenylphosphino)methylamine ligand: Synthesis, molecular structure and catalytic activity

Gumgum, Bahattin
Özkar, Saim
ŞAHİN, Ertan
Reaction of Ph2PNHCH2-C4H3S with [Ru(eta(6)-p-cymene)(mu-Cl)Cl](2), [Ru(eta(6)-benzene)(mu-Cl)Cl](2), [Rh(mu-Cl)(cod)](2) and [Ir(eta(5)-C5Me5)(mu-Cl)Cl](2) yields complexes [Ru(Ph2PNHCH2-C4H3S)(eta(6)-p-cymene)Cl-2], 1, [Ru(Ph2PNHCH2-C4H3S)(eta(6)-benzene)Cl-2], 2, [Rh(Ph2PNHCH2-C4H3S)(cod)Cl], 3 and [Ir(Ph2PNHCH2-C4H3S)(eta(5)-C5Me5)Cl-2], 4, respectively. All complexes were isolated from the reaction solution and fully characterized by analytical and spectroscopic methods. The structure of [Ru(Ph2PNHCH2-C4H3S)(eta(6)-benzene)Cl-2], 2 was also determined by single crystal X-ray diffraction. 1-4 are suitable precursors forming highly active catalyst in the transfer hydrogenation of a variety of simple ketones. Notably, the catalysts obtained by using the ruthenium complexes [Ru(Ph2PNHCH2-C4H3S)(eta(6)-p-cymene)Cl-2], 1 and [Ru(Ph2PNHCH2-C4H3S)(eta(6)-benzene)Cl-2], 2 are much more active in the transfer hydrogenation converting the carbonyls to the corresponding alcohols in 98-99% yields (TOF <= 200 h(-1)) in comparison to analogous rhodium and iridium complexes.


Enantioselective aza-Henry reaction of t-Boc protected imines and nitroalkanes with bifunctional squaramide organocatalysts
Susam, Zeynep Dilşad; Tanyeli, Cihangir (2017-05-07)
An organocatalytic asymmetric aza-Henry reaction of t-Boc protected imines with nitroalkanes has been established by chiral acid-base type bifunctional Cinchona alkaloid/squaramide organocatalysts. The cooperation of a quinine motif as a base and sterically encumbered squaramide (H-bond donor) enabled mostly complete conversion of a range of reactants into the corresponding aza-Henry products at room temperature with good selectivities (up to 91% ee with 10 mol% catalyst loading).
Highly selective intermolecular one-pot three component 1,3-dipolar cycloaddition reaction of aldehydes, with phosphonates and proline
Subasi, N. Tuna; Yalcinkaya, Hatice; Demir, Ayhan Gürbüz (2017-07-27)
The use of L-proline to act as an organocatalyst in the aldol reaction of acylphosphonates and non enolizable aldehydes failed; however, it reacted with the aldehydes to afford azomethine ylides after decarboxylation that in turn underwent 1,3-dipolar cycloaddition with the acylphosphonates to form a bicyclic hexahydropyrrolo[1,2-c]oxazol-1-ylphosphonates in good yield. No azomethine ylide formation was observed on the reaction of acylphosphonates with proline.
Thermal polymerization of bis(4-fluoro-2,6-dibromophenolato)bis(pyridine)copper(II) complex in solution and in solid state
Kisakurek, D; Akbas, M; Bilir, N (Wiley, 1998-02-01)
The synthesis of the bis(4-fluoro-2,6-dibromophenolato)bis(pyridine)copper(II) complex was achieved from aqueous solution, and its characterization was performed by means-of IR and CHN elemental analysis. Thermal polymerization of this complex was carried out in toluene and in solid state. The structural analysis of the polymers was performed with H-1 NMR, C-13 NMR and FTIR analysis; the glass transition temperature was found to be at 160 degrees C. 4-Fluoro-2,6-dibromophenolate, with the non-chelating liga...
Light mesons: pi, eta, and omega and exotic low mass meson production at intermediate energies in nucleon-nucleon scattering
Tatischeff, B; Yonnet, J; Rekalo, MP; Boivin, M; Comets, MP; Courtat, P; Gacougnolle, R; Le Bornec, Y; Loireleux, E; Reide, F; Willis, N (2000-11-01)
The reaction (p) over barp-->ppX was studied at three energies (T-p=1520, 1805, and 2100 MeV) and at several angles between 0 degrees and 17 degrees in the lab. The analyzing powers and differential cross sections of light meson production, X = pi, eta, and omega, were measured. The c.m. angular range varied between 0 degrees and 180 degrees where the incident energy combined with the experimental acceptance allow both forward and backward kinematical solutions. A theoretical analysis based on s-channel con...
Hydrocarbon-Soluble, Isolable Ziegler-Type Ir(0)(n) Nanoparticle Catalysts Made from [(1,5-COD)Ir(mu-O2C8H15)](2) and 2-5 Equivalents of AlEt3: Their High Catalytic Activity, Long Lifetime, and AlEt3-Dependent, Exceptional, 200 degrees C Thermal Stability
Hamdemir, Isil K.; Özkar, Saim; Yih, Kuang-Hway; Mondloch, Joseph E.; Finke, Richard G. (2012-04-01)
Hydrocarbon-solvent-soluble, isolable, Ziegler-type Ir(0)(n) nanoparticle hydrogenation catalysts made from the crystallo-graphically characterized [(1,5-COD)Ir(mu-O2C8H15)](2) precatalyst and 2-5 equiv of AlEt3 (>= 2 equiv of AlEt3 being required for the best catalysis and stability, vide infra) are scrutinized for their catalytic properties of (1) their isolability and then redispersibility without visible formation of bulk metal; (2) their initial catalytic activity of the isolated nanoparticle catalyst ...
Citation Formats
M. AYDEMİR et al., “Organometallic ruthenium, rhodium and iridium complexes containing a P-bound thiophene-2-(N-diphenylphosphino)methylamine ligand: Synthesis, molecular structure and catalytic activity,” JOURNAL OF ORGANOMETALLIC CHEMISTRY, pp. 2584–2588, 2011, Accessed: 00, 2020. [Online]. Available: