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Selective Carbon–Carbon Bond Activation of Oxirane by a Bisphosphine Pt(0) Complex—A Theoretical Study

26-Jul-2015 | Philipp N. Plessow; Jorge J. Carbó; Ansgar Schäfer; Peter Hofmann, Organometallics, 2015

Platinum(0) complexes with the chelate ligand bis(di-tert-butylphosphino)methane, tBu2P-CH2-PtBu2 (dtbpm), generated in solution from appropriate precursors, are the only known transition metal species that selectively activate epoxides (oxiranes) by inserting the Pt fragment into their ...


Carboxylic Group-Assisted Proton Transfer in Gold-Mediated Thiolation of Alkynes

22-Jul-2015 | Sergey S. Zalesskiy; Victor N. Khrustalev; Alexandr Yu. Kostukovich; Valentine P. Ananikov, Organometallics, 2015

Combined experimental and theoretical studies revealed a complex mechanistic picture in which the carboxylic group-assisted proton transfer from acetic acid to an alkyne molecule is the key step in the unique gold-mediated alkyne transformation that leads to the formation of gem-disubstituted ...


Reactivity of an Unsaturated Iridium(III) Phosphoramidate Complex, [Cp*Ir{κ2-N,O}][BArF4]

22-Jul-2015 | Marcus W. Drover; Heather C. Johnson; Laurel L. Schafer; Jennifer A. Love; Andrew S. Weller, Organometallics, 2015

The three-legged piano stool complex [Cp*Ir(κ2-N,O-Xyl(N)P(O)(OEt)2)(Cl)], [1] (Cp* = η5-C5Me5, Xyl = 2,6-dimethylphenyl), was prepared from reaction of 0.5 equiv of [Cp*IrCl2]2 with the sodiated phosphoramidate ligand Na[Xyl(N)P(O)(OEt)2]. Treatment of [1] with Na[BArF4], [BArF4] = ...


C–H versus O–H Bond Activation in Phosphino-alcohol Ligands: Synthesis of the α-Hydroxy-alkyl Ruthenium(II) Derivatives [RuCl{κ2(P,C)-Ph2PC6H4C(R)OH}(η6-arene)]

21-Jul-2015 | Alba E. Díaz-Álvarez; Cristian Vidal; Francisco J. Suárez; Josefina Díez; Victorio Cadierno; Pascale Crochet, Organometallics, 2015

The coordination of the phosphino-alcohol ligands 2-Ph2PC6H4CH(R)OH (R = H, Me) onto an arene-ruthenium(II) fragment gave rise to the formation of complexes of general formula [RuCl2{2-Ph2PC6H4CH(R)OH}(η6-arene)] (R = H, arene = C6H6 (3a), p-cymene (3b), mesitylene (3c), C6Me6 (3d); R = Me, arene ...


PBiP Pincer Complexes of Platinum, Palladium, and Iridium Featuring Metal–Metal Bonds Synthesized by Oxidative Addition of Bismuth–Halide Bonds

20-Jul-2015 | Carolin Tschersich; Beatrice Braun; Christian Herwig; Christian Limberg, Organometallics, 2015

The compound BiCl(o-PPh2-C6H4)2, PBiP-Cl, which in previous work had been shown to form complexes with pronounced M→Bi character, when metal(I) ions of group 11 or PtII and PdII ions were coordinated, behave differently in contact with late metal atoms in low oxidation states, known to easily ...


Thermally Stable Diazoalkane Derivatives of the Unsaturated Ditungsten Hydride [W2Cp2(H)(μ-PCy2)(CO)2]

20-Jul-2015 | M. Angeles Alvarez; M. Esther García; Daniel García-Vivó; Estefanía Huergo; Miguel A. Ruiz; M. Fernanda Vega, Organometallics, 2015

The title compound reacted rapidly with N2CH(SiMe3) at room temperature to give the electron-precise hydride [W2Cp2(H)(μ-PCy2)(CO)2{N-N2CH(SiMe3)}] (W–W = 2.9907(5) Å), in which the diazoalkane molecule is N-bound strongly to one of the metal centers, formally acting as an imido-like ...


Different Coordination Modes of the Ph2PCsp3PPh2 Pincer Ligand in Rhodium Complexes as a Consequence of Csp3–H Metal Interaction

08-Jul-2015 | Janet Arras; Hansjörg Speth; Hermann A. Mayer; Lars Wesemann, Organometallics, 2015

Starting from commercially available 4,4′-di-tert-butyldiphenylmethane the pincer ligand bis(4-tert-butyl-2-(diphenylphosphino)phenyl)methane (PCP) was prepared in two steps in moderate yield. Treatment of a solution of RhCl3·3H2O in a mixture of isopropyl alcohol and toluene with equimolar ...


Air-Stable NNS (ENENES) Ligands and Their Well-Defined Ruthenium and Iridium Complexes for Molecular Catalysis

29-Jun-2015 | Pavel A. Dub; Brian L. Scott; John C. Gordon, Organometallics, 2015

We introduce ENENES, a new family of air-stable and low-cost NNS ligands bearing NH functionalities of the general formula E(CH2)mNH(CH2)nSR, where E is selected from −NC4H8O, −NC4H8, or −N(CH3)2, m and n = 2 and/or 3, and R = Ph, Bn, Me, or SR (part of a thiophenyl fragment). The preparation and ...


Cyclometalated Phosphinine–Iridium(III) Complexes: Synthesis, Reactivity, and Application as Phosphorus-Containing Water-Oxidation Catalysts

10-Jun-2015 | Leen E. E. Broeckx; Alberto Bucci; Cristiano Zuccaccia; Martin Lutz; Alceo Macchioni; Christian Müller, Organometallics, 2015

The novel phosphinine-based coordination compound [Cp*Ir(P∧C)(CH3CN)]CF3SO3 (P∧C = cyclometalated 2,4,6-triphenylphosphinine) could be synthesized by chloride abstraction from [Cp*Ir(P∧C)Cl] with AgOSO2CF3 and crystallographically characterized. It turned out that this species is the first ...


Stabilization of an Electron-Unsaturated Pd(I)–Pd(I) Unit by Double Hemichelation

09-Jun-2015 | Christophe Werlé; Lydia Karmazin; Corinne Bailly; Louis Ricard; Jean-Pierre Djukic, Organometallics, 2015

The competition between conventional coordination and hemichelation of a Pd(II) center of three different palladacycles was probed by reacting the tricarbonyl(η6-3-phenylprop-1-enyl)chromium anion with μ-chloro-bridged palladacycles. Structural X-ray diffraction analysis indicates that the main ...


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