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Synthesis and properties of dinuclear Ru(II)/Os(II) complexes based on a heteroditopic phenanthroline-terpyridine bridging ligand

The synthesis and characterization of a series of mono- and dinuclear ruthenium(II) and osmium(II) polypyridyl complexes based on the heteroditopic bridging ligand PT are reported. This ligand incorporates bidentate phen (1,10-phenanthroline) and terdentate tpy (2,2?:6?,2?- terpyridine) units directly connected by their 3 and 5 positions, respectively. The dinuclear complexes have been synthesized via a Pd(0) catalyzed cross-coupling reaction between a bromo-substituted Ru-phen complex and a tpy derivative incorporating a boronate ester, followed by Ru(II) or Os(II) complexation. The compounds obtained are fully characterized using spectroscopic and electrochemical measurements. The electrochemical studies do not yield any evidence for interaction between the two metal centers in the dinuclear compounds. Emission studies indicate, however, energy transfer from the phen moiety to the tpy center. For the ruthenium/osmium species, this process is relatively slow, resulting in a dual emission. The emission of the mononuclear ruthenium compound is enhanced by the addition of Zn(II).

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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NOVEL 4-AMINO-6-(PYRIDYL AND 2-SUBSTITUTEDPHENYL)-PICOLINATES AND 6-AMINO-2-(PYRIDYL AND 2-SUBSTITUTEDPHENYL)-PYRIMIDINE-4-CARBOXYLATES AND THEIR USE AS HERBICIDES

4-amino-6-(pyridyl and 2-substitutedphenyl)-picolinic acids and their derivatives; 6-amino-2-(pyridyl and 2-substitutedphenyl)-pyrimidine-4-carboxylates and their derivatives; and methods of using the same as herbicides.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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An efficient synthesis of 4-arylquinolin-2(1 H)-ones and 3-alkenyl-4-arylquinolin-2(1 H)-one using a Pd/NiFe2O 4-catalyzed consecutive Heck reaction

A convenient one-pot method for the synthesis of 4-arylquinolin-2(1H)-ones and 4-arylcoumarins has been described. The successive Heck reaction on substituted 2-iodoaniline and 2-iodophenol catalyzed by a Pd/nickel ferrite catalyst followed by in situ cyclization was the key step. The scope of this methodology was extended to the synthesis of bioactive 3-alkenyl derivatives of 4-arylquinolin-2(1H)-ones.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Nonsymmetrical 3,4-dithienylmaleimides by cross-coupling reactions with indium organometallics: Synthesis and photochemical studies

The synthesis and photochemical study of novel nonsymmetrical 1,2-dithienylethenes (DTEs) with a maleimide bridge have been carried out. The synthetic approach to the DTEs was based on successive selective palladium-catalyzed cross-coupling reactions of 5-susbtituted-2-methyl-3-thiophenyl indium reagents with 3,4-dichloromaleimides. The required organoindium reagents were prepared from 2-methyl-3,5-dibromothiophene by a selective (C-5) coupling reaction with triorganoindium compounds (R3In) and subsequent metal-halogen exchange. The coupling reactions usually gave good yields and have a high atom economy with substoichiometric amounts of R3In. The results of photochemical studies show that these novel dithienylmaleimides undergo a photocyclization reaction upon irradiation in the UV region and a photocycloreversion after excitation in the visible region, thus they can be used as photochemical switches. ON-OFF operations can be repeated in successive cycles without appreciable loss of effectiveness in the process.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Controlling electron transfer in donor-bridge-acceptor molecules using cross-conjugated bridges

Photoinitiated charge separation (CS) and recombination (CR) in a series of donor-bridge-acceptor (D-B-A) molecules with cross-conjugated, linearly conjugated, and saturated bridges have been compared and contrasted using time-resolved spectroscopy. The photoexcited charge transfer state of 3,5-dimethyl-4-(9-anthracenyl)julolidine (DMJ-An) is the donor, and naphthalene-1,8:4,5-bis(dicarboximide) (NI) is the acceptor in all cases, along with 1,1-diphenylethene, trans-stilbene, diphenylmethane, and xanthone bridges. Photoinitiated CS through the cross-conjugated 1,1-diphenylethene bridge is about 30 times slower than through its linearly conjugated trans-stilbene counterpart and is comparable to that observed through the diphenylmethane bridge. This result implies that cross-conjugation strongly decreases the pi orbital contribution to the donor-acceptor electronic coupling so that electron transfer most likely uses the bridge sigma system as its primary CS pathway. In contrast, the CS rate through the cross-conjugated xanthone bridge is comparable to that observed through the linearly conjugated trans-stilbene bridge. Molecular conductance calculations on these bridges show that cross-conjugation results in quantum interference effects that greatly alter the through-bridge donor-acceptor electronic coupling as a function of charge injection energy. These calculations display trends that agree well with the observed trends in the electron transfer rates.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Synthesis of versatile nonsymmetric amine- and boron-functionalized troeger’s base derivatives, including a troeger’s base amino acid

Troeger’s base is a building block with a unique rigidity and geometry that has an increasing number of applications in a variety of nanoscale chemistry projects. This paper describes the facile synthesis of a set of Troeger’s base derivatives that have lost their C2 symmetry by virtue of having each ring differentiated, and contain amine, carboxylate, halogen, and/or boronate substituents to enable a large number of different cross-coupling and amide coupling reactions. We also describe the synthesis and preliminary chiral resolution of a new Troeger’s base amino acid building block. Novel, nonsymmetric Troeger’s base compounds have been synthesized that are convenient starting points for further elaboration by cross-coupling and amide coupling reactions. Examples include the preparation of a novel Troeger’s base amino acid. Copyright

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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THERAPEUTICALLY ACTIVE COMPOUNDS AND THEIR METHODS OF USE

Provided are compounds useful for treating cancer and methods of treating cancer comprising administering to a subject in need thereof a compound described herein.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Palladium-Catalyzed Cascade Cyclization of Alkene-Tethered Aryl Halides with o-Bromobenzoic Acids: Access to Diverse Fused Indolo[2,1- A[isoquinolines

A novel palladium-catalyzed cascade cyclization of alkene-tethered aryl halides with o-bromobenzoic acids is described, which provides an efficient avenue for building various fused hexacyclic scaffolds containing indolo[2,1-a]isoquinoline in moderate to excellent yield. The method enables the construction of three C-C bonds through an intramolecular carbopalladation, C-H activation, and a decarboxylation sequence. Furthermore, dihydrocyclohepta[de]naphthalene-fused indolo[2,1-a]isoquinolines can be synthesized in moderate yield by constructing a seven-membered ring.

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Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Design of cationic conjugated polyelectrolytes for DNA concentration determination

Cationic conjugated polyelectrolytes poly110 and poly1 20 were designed, synthesized, and characterized with the anticipation of function in the determination of double-stranded DNA concentration [dsDNA]. Their structures contain a pi-delocalized optically active backbone composed of phenylene-fluorene segments copolymerized with 2,1,3-benzothiadiazole (BT) units and charged pendant groups that allow excellent solubility in water. The subscript in poly1x refers to the molar percent of BT units in the chain. Addition of dsDNA to poly110 or poly120 results in a change in the color of emission from blue to green. These spectral changes can be treated to obtain the parameter delta, which can be used to generate calibration curves that indicate [dsDNA]. Analysis of photoluminescence spectra reveals that dsDNA addition gives rise to more efficient FRET from blue emitting segments to the BT sites, an increase in the BT emission quantum yield, and partial quenching of the phenylene-fluorene segments. Studies were also carried out to maximize the range of [dsDNA] determination. We find that by combining the response from two different initial concentrations of poly110, it is possible to generate calibration curves that respond with a difference in [dsDNA] of over 7 orders of magnitude.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Paracyclophane-based monophosphine ligand for palladium-catalyzed cross-coupling reactions of aryl chlorides

A new [2.2]paracyclophane-based electron-rich and sterically bulky monophosphine ligand has been synthesized by an efficient and straightforward method. When combined with palladium, this ligand shows excellent performance in the Buchwald-Hartwig amination and Suzuki-Miyaura coupling reactions of various aryl chlorides. In both types of reactions, ortho-substituted, deactivated aryl chlorides are shown to be viable substrates. However, the Suzuki-Miyaura coupling appears to be easier, with palladium loading at 0.1 mol% being feasible. The Royal Society of Chemistry 2009.

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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method