A catalytic system for titanocene-catalyzed epoxide hydrosilylation is described. It features a straightforward preparation of titanocene hydrides that leads to a reaction with low catalyst loading, high yields, and high selectivity of radical reduction. The mechanism was studied by a suite of methods, including kinetic studies, EPR spectroscopy, and computational methods. An unusual resting state leads to the observation of an inverse rate order with respect to the epoxide.
Two new catalytic systems for hydrogen-atom transfer (HAT) catalysis involving the N-H bonds of titanocene(III) complexes with pendant amide ligands are reported. In a monometallic system, a bifunctional catalyst for radical generation and reduction through HAT catalysis depending on the coordination of the amide ligand is employed. The pendant amide ligand is used to activate Crabtree's catalyst to yield an efficient bimetallic system for radical generation and HAT catalysis.
Barbiturate dyes containing either a dipolar or polarizable chromophoric system have been synthesized and their solvatochromism investigated. The effect of specific and non-specific solvent interactions on the position of their UV/Vis absorption bands has been evaluated by using the Kamlet-Taft
Theoretical description of phosphorescence lifetimes in the condensed phase requires a method that takes into account both spin-orbit coupling and solvent-solute interactions. To obtain such a method, we have coupled our recently developed two-component coupled-cluster method with singles and approximated doubles to a polarizable environment. With this new method, we investigate how different solvents effect the electronic phosphorescence energies and lifetimes of 4H-pyran-4-thione.
The supramolecular complex formation by cooperativehydrogen bonding of a highly dipolar barbiturate dye and 2,6‐diacetamidopyridine is shown to have a marked effect on the reactivity of the barbiturate. The increase of both Lewis acidity and electrophilicity by hydrogen bonding is demonstrated by thermodynamic and kinetic studies using the electrophile–nucleophile recombination reaction with cyanide.
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