Browsing by Subject "room-temperature"

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Bis(Imino)Acenaphthene (BIAN)-Supported Palladium(II) Carbene Complexes as Effective C-C Coupling Catalysts and Solvent Effects in Organic and Aqueous Media
(2014) Crawford, Katherine A.; Cowley, Alan H.; Humphrey, Simon M.; Crawford, Katherine A.; Cowley, Alan H.; Humphrey, Simon M.
The synthesis and catalytic properties of two new 1,2-acenaphthenyl N-heterocyclic carbene-supported palladium(II) catalysts are presented. The acenaphthenyl carbene has been prepared with mesityl or 1,5-diisopropyl N-aryl substituents. Comprehensive catalytic studies for the Suzuki coupling of aryl halides with aryl boronic acids have been conducted. In general, the diisopropyl-functionalised catalyst showed superior selectivity and reactivity. A comparison of the catalytic performances in dichloromethane, toluene and water at low temperatures (30- 40 degrees C) is also presented. Both catalysts were proficient in the homogeneous Suzuki coupling of aryl iodides, bromides and chlorides with boronic acids in dichloromethane. Similar reactions in water led to the formation of insoluble colloidal catalytic species that still exhibited high activity in the Suzuki reaction with aryl chlorides. Reactions performed in toluene showed intermediate results; partial catalyst decomposition led to concomitant homogeneous and heterogeneous catalysis. The heterogeneous palladium precipitates could be easily recovered by filtration and reactivated for subsequent use. Activation energies determined for aryl bromide-based Suzuki reactions were found to be in the range of 159-171 kJ mol(-1) in organic solvents and 111-116 kJ mol(-1) in water. The corresponding activation energy for the aryl chloride was found to be 322 kJ mol(-1) in water.
Palladium-Catalyzed Direct Beta-Arylation of Ketones with Diaryliodonium Salts: A Stoichiometric Heavy Metal-Free and User-Friendly Approach
(2015-06) Huang, Zhonxing X.; Sam, Quynh P.; Dong, Guangbin B.; Huang, Zhonxing X.; Sam, Quynh P.; Dong, Guangbin B.
We herein report a new protocol for the Pd-catalyzed beta-arylation of ketones without stoichiometric heavy metals. Widely accessible diaryliodonium salts are used as both the oxidant and aryl source. This tandem redox catalysis merges ketone dehydrogenation and conjugate addition without an additional oxidant or reductant. This transformation features the use of a unique bis-N-tosylsulfilimine ligand and the combination of potassium trifluoroacetate/trifluoroacetic acid to maintain an appropriate acidity of the reaction medium. The reaction tolerates both air and moisture, and shows a broad substrate scope. Kinetics studies, along with filtration and poisoning tests, support the involvement of palladium nanoparticles in the catalysis.
Synthesis and Study of Olefin Metathesis Catalysts Supported by Redox-Switchable Diaminocarbene 3 Ferrocenophanes
(2013-07) Varnado, C. Daniel; Rosen, Evelyn L.; Collins, Mary S.; Lynch, Vincent M.; Bielawski, Christopher W.; Varnado, C. Daniel; Rosen, Evelyn L.; Collins, Mary S.; Lynch, Vincent M.; Bielawski, Christopher W.
A redox-switchable ligand, N,N'-dimethyldiaminocarbene[3]ferrocenophane (5), was synthesized and incorporated into a series of Ir- and Ru-based complexes. Electrochemical and spectroscopic analyses of (5) Ir(CO)(2)Cl (15) revealed that 5 displayed a Tolman electronic parameter value of 2050 cm(-1) in the neutral state and 2061 cm(-1) upon oxidation. Moreover, inspection of X-ray crystallography data recorded for (5) Ir(cis,cis-1,5-cyclooctadiene)Cl (13) revealed that 5 was sterically less bulky (%V-Bur = 28.4) than other known diaminocarbene[3]ferrocenophanes, which facilitated the synthesis of (5)(PPh3)Cl2Ru-(3-phenylindenylid-1-ene) (18). Complex 18 exhibited quasi-reversible electrochemical processes at 0.79 and 0.98 V relative to SCE, which were assigned to the Fe and Ru centers in the complex, respectively, based on UV-vis and electron pair resonance spectroscopic measurements. Adding 2,3-dichloro-5,6-dicyanoquinone over the course of a ring-opening metathesis polymerization of cis, cis-1,5-cyclooctadiene catalyzed by 18 ([monomer](0)/[18](0) = 2500) reduced the corresponding rate constant of the reaction by over an order of magnitude (pre-oxidation: k(obs) = 0.045 s(-1); post-oxidation: k(obs) = 0.0012 s(-1)). Subsequent reduction of the oxidized species using decamethylferrocene restored catalytic activity (post-reduction: k(obs) = up to 0.016 s(-1), depending on when the reductant was added). The difference in the polymerization rates was attributed to the relative donating ability of the redox-active ligand (i.e., strongly donating 5 versus weakly donating 5(+)) which ultimately governed the activity displayed by the corresponding catalyst.