Under visible-light irradiation, the gold-catalyzed intermolecular difunctionalization of alkynes with aryl diazonium salts in methanol affords a variety of α-aryl ketones in moderate to good yields. In contrast to previous reports on gold-catalyzed reactions that involve redox cycles, no external oxidants or photosensitizers are required. The reaction proceeds smoothly under mild reaction conditions and shows broad functional-group tolerance. Further applications of this method demonstrate the general applicability of the arylation of a vinyl gold intermediate instead of the commonly used protodemetalation step. This step provides facile access to functionalized products in one-pot processes. With a P,N-bidentate ligand, a stable aryl gold(III) species was obtained, which constitutes the first direct experimental evidence for the commonly postulated direct oxidative addition of an aryl diazonium salt to a pyridine phosphine gold(I) complex.

Photosensitizer-Free Visible-Light-Mediated Gold-Catalyzed 1,2-Difunctionalization of Alkynes

Recent progress on nickel-based systems for ethylene oligo-/polymerization catalysis

This Review showcases the ability of bi- and tridentate ligands to stabilize gold in high oxidation states through the formation of mono- and biscyclometalated gold(III) complexes. In-depth studies on the synthesis, intrinsic reactivity, catalytic relevance, and photophysical properties of stabilized gold(III) species have been carried out, setting the stage for exciting developments in various research areas, such as catalysis, inorganic and bioinorganic chemistry, ligand design, and materials science.

Cyclometalated Gold(III) Complexes: Synthesis, Reactivity, and Physicochemical Properties

Gold‐katalysierte 1,2‐Difunktionalisierung von Alkinen mit sichtbarem Licht ohne zusätzlichen Photosensibilisator

The stoichiometric reactions of 5,6,7,8-tetrahydrocycloheptapyridin-9-one (cycloheptapyridin-9-one) with various anilines lead to corresponding mixtures of 9-aryliminocycloheptapyridine and the isomeric 9-arylamino-5,6,7-trihydrocycloheptapyridine derivatives; these compounds further reacted with nickel dichloride to form 9-aryliminocycloheptapyridyl nickel chlorides, respectively. The new organic compounds were analyzed by the NMR measurements, and all the organic and complex compounds were characterized by the FT-IR spectroscopy and elemental analysis. In addition, the molecular structures of representative nickel complexes Ni1 and Ni3, determined by means of single-crystal X-ray diffraction, were found to be binuclear dimers with distorted square-pyramidal geometry around the nickel centers. On activation with either ethylaluminium sesquichloride (Et3Al2Cl3) or methylaluminoxane (MAO), all nickel complex pre-catalysts exhibited high activities of up to 7.80 × 106 g PE mol−1 (Ni) h−1 toward ethylene polymerization and produced highly branched polyethylenes in narrow polydispersity. The title nickel complexes showed comparable activities with 8-arylimino-5,6,7-trihydroquinolyl nickel analogues; whilst both exhibited higher activities than did the 2-iminopyridyl nickel analogues due to the enhancement of the ring-tension of cyclic-fused pyridine derivatives.

H. Kooijman

Papers

Nickel and palladium complexes of pyridine-phosphine ligands as ethene oligomerization catalysts

Nickel and palladium complexes of new pyridine-phosphine ligands and their use in ethene oligomerization