65 research outputs found
Versatile Coordination of Cyclopentadienyl-Arene Ligands and Its Role in Titanium-Catalyzed Ethylene Trimerization
Cationic titanium(IV) complexes with ansa-(η5-cyclopentadienyl,η6-arene) ligands were synthesized and characterized by X-ray crystallography. The strength of the metal-arene interaction in these systems was studied by variable-temperature NMR spectroscopy. Complexes with a C1 bridge between the cyclopentadienyl and arene moieties feature hemilabile coordination behavior of the ligand and consequently are active ethylene trimerization catalysts. Reaction of the titanium(IV) dimethyl cations with CO results in conversion to the analogous cationic titanium(II) dicarbonyl species. Metal-to-ligand backdonation in these formally low-valent complexes gives rise to a strongly bonded, partially reduced arene moiety. In contrast to the η6-arene coordination mode observed for titanium, the more electron-rich vanadium(V) cations [cyclopentadienyl-arene]V(NiPr2)(NC6H4-4-Me)+ feature η1-arene binding, as determined by a crystallographic study. The three different metal-arene coordination modes that we experimentally observed model intermediates in the cycle for titanium-catalyzed ethylene trimerization. The nature of the metal-arene interaction in these systems was studied by DFT calculations.
Increasing the Reactivity of Vaska’s Compound. Oxidative Addition of Chlorobenzene at Ambient Temperature
Pd-Catalyzed Conversion of Aryl Chlorides, Triflates, and Nonaflates to Nitroaromatics
An efficient Pd catalyst for the transformation of aryl chlorides, triflates, and nonaflates to nitroaromatics has been developed. This reaction proceeds under weakly basic conditions and displays a broad scope and excellent functional group compatibility. Moreover, this method allows for the synthesis of aromatic nitro compounds that cannot be accessed efficiently via other nitration protocols. Mechanistic insight into the transmetalation step of the catalytic process is also reported.National Institutes of Health (U.S.) (GM-58160)BASFMerck & Co. (Fellowship)William Asbornsen Albert Memorial Fund (Fellowship
Amination of Aryl Halides: Quantitative Assessment of Stoichiometric and Catalytic Kinetic Studies
Effect of Ligand Steric Properties and Halide Identity on the Mechanism for Oxidative Addition of Haloarenes to Trialkylphosphine Pd(0) Complexes
Palladium-Catalyzed Regioselective Arylation of 1,1,3-Triaryl-2-azaallyl Anions with Aryl Chlorides
Mechanistic Significance of the Si–O–Pd Bond in the Palladium-Catalyzed Cross-Coupling Reactions of Arylsilanolates
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