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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 ...

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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 ...

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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] = ...

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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 ...

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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 ...

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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 ...

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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 ...

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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 ...

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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 ...

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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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