Published in Organometallics
Oxidative addition of aryl halides to Ni(0) is a ubiquitous elementary step in cross-coupling and related reactions, usually producing a square-planar Ni(II)–aryl intermediate. Here we show that a triphosphine ligand supports oxidative addition at a tris-ligated Ni(0) center to cleanly form stable five-coordinate Ni(II)–aryl compounds. Kinetic and ...
Published in Organometallics
Titanium(IV) complexes of amino-tris(phenolate) ligands (LTiX, X = chloride, isopropoxide) together with bis(triphenylphosphine)iminium chloride (PPNCl) are active catalyst systems for the ring-opening copolymerization of carbon dioxide and cyclohexene oxide. They show moderate activity, with turnover frequency values of ∼60 h–1 (0.02 mol % of cata...
Published in Organometallics
Vinyl sulfoxides are an important functional group used in a wide range of organic transformations. Here, we use [IrCl(COD)(IMes)] where IMes = 1,3-bis(2,4,6-trimethyl-phenyl)imidazole-2-ylidene and COD = cis , cis -1,5-cyclooctadiene to rapidly hydrogenate phenylvinylsulfoxide. We use para -hydrogen-induced hyperpolarization (PHIP) to follow this ...
Published in Organometallics
The catalytic asymmetric transfer hydrogenation (ATH) of ketones is a powerful methodology for the practical and efficient installation of chiral centers. Herein, we describe the synthesis, characterization, and catalytic application of a series of manganese complexes bearing simple chiral diamine ligands. We performed an extensive experimental and...
Published in Organometallics
UV-induced photochemical transformations of the paramagnetic [Cr(CO)4(Ph2PCH2CH2CH2PPh2)]+ complex (abbreviated [Cr(CO)4(dppp)]+) in dichloromethane was investigated by CW EPR spectroscopy. Room-temperature UV irradiation results in the rapid transformation of [Cr(CO)4(dppp)]+ into trans -[Cr(CO)2(dppp)2]+. However, low-temperature (77–120 K) UV ir...
Published in Organometallics
In this communication we report a convenient, as short as possible synthesis of aminocobaltocenium hexafluoridophosphate, a very useful compound for further functionalization in cobaltocenium chemistry. Via vicarious nucleophilic substitution of hydrogen of cobaltocenium hexafluoridophosphate with 1,1,1-trimethylhydrazinium iodide as nucleophile be...
Published in Organometallics
Highly enantioselective Hiyama cross-coupling reactions have been achieved through rhodium(I)-catalyzed dynamic kinetic asymmetric transformations between aryl siloxanes and cyclic racemic allyl halides. This process affords valuable enantiomerically enriched aryl-substituted cyclic allyl products and is compatible with heterocyclic allyl chloride ...
Published in Organometallics
Synthesis of a number of disiloxane containing cyclo- and bicyclooligosilanes is described starting from the dipotassium 1,5-oligosiloxanylene diide derived from 1,3-bis[tris(trimethylsilyl)silyl]tetramethyldisiloxane. In addition, the use of this particular fragment as ligand for zinc and group 4 metallocene complexes was studied. Both types of co...
Published in Organometallics
Published in Organometallics
