Synergistic effect of coordinating interface and promoter for enhancing ammonia synthesis activity of Ru@N-C catalyst.

Triruthenium dodecacarbonyl (Ru3(CO)12) was applied to prepare the Ru-based ammonia synthesis catalysts. The catalyst obtained from this precursor exhibited higher activity than the other Ru salts owing to its unique atomic reorganization under mild temperatures. Herein, Ru3(CO)12 as a guest metal source incorporated into the pore of ZIF-8 formed the Ru@N-C catalysts. The results indicated that the Ru nanoparticle (1.7 nm) was dispersed in the confined N coordination environment, which can increase the electron density of the Ru nanoparticles to promote N[triple bond, length as m-dash]N bond cleavage. The promoters donate the basic sites for transferring the electrons to Ru nanoparticles, further enhancing ammonia synthesis activity. Ammonia synthesis investigations revealed that the obtained Ru@N-C catalysts exhibited obvious catalytic activity compared with the Ru/AC catalyst. After introducing the Ba promoter, the 2Ba-Ru@N-C(450) catalyst exhibited the highest ammonia synthesis activity among the catalysts. At 360 °C and 1 MPa, the activity of the 2Ba-Ru@N-C(450) is 16 817.3 µmol h-1 gRu-1, which is 1.1, 1.6, and 2 times higher than those of 2Cs-Ru@N-C(450) (14 925.4 µmol h-1 gRu-1), 2K-Ru@N-C(450) (10 736.7 µmol h-1 gRu-1), and Ru@N-C(450) (8604.2 µmol h-1 gRu-1), respectively. A series of characterizations were carried out to explore the 2Ba-Ru@N-C(450) catalysts, such as H2-TPR, XPS, and NH3-TPD. These results suggest that the Ba promoter played the role of an electronic and structural promoter; moreover, it can promote the NH3 desorption from the Ru nanoparticles.

Palladium-catalyzed aryl C-H bonds activation/acetoxylation utilizing a bidentate system.

A palladium-catalyzed aryl C-H bonds activation/acetoxylation reaction utilizing a bidentate system has been explored. This transformation has been applied to a wide array of pyridine and 8-aminoquinoline derivatives and it exhibits excellent functional group tolerance.

One-pot synthesis of highly substituted aromatic amine derivatives via Pd-catalyzed aminobenzannulation reaction.

A novel and convenient Pd(0)-catalyzed carboannulation with propargylic compounds for the synthesis of highly substituted aromatic amine derivatives in a one-pot operation was developed. In this process, a significant breakthrough in aminobenzannulation is observed. Moreover, the reaction appears to be very general and suitable for a variety of amines.

Highly regio- and stereoselective synthesis of indene and benzo[b]furan derivatives via a Pd-catalyzed carboannulation of propargyl carbonates with nucleophiles.

A new and efficient synthesis of indene and benzo[b]furan derivatives has been achieved via Pd-catalyzed carboannulation of propargyl carbonates with nucleophiles in good to excellent yields with high regio- and stereoselectivity. A novel sequence of nucleophilic attack is observed, and a possible mechanism is proposed.

New insight into Ni(II)-catalyzed cyclization reactions of propargylic compounds with soft nucleophiles: novel indenes formation.

We have disclosed a very nice advance of nickel(II)-catalyzed carboannulation reactions. Highly substituted indene derivatives are readily prepared in moderate to excellent yields under very mild reaction conditions in air via a nickel(II)-catalyzed cyclization of propargylic compounds with soft nucleophiles.

Highly regioselective synthesis of indene derivatives including an allene functional group via Pd/C-catalyzed cyclization reaction in air.

Indene derivatives including an allene functional group are readily prepared in moderate to excellent yields with high regioselectivity under very mild reaction conditions by the Pd/C-catalyzed reaction of propargylic compounds. The resulting products can be further elaborated using Pd-catalyzed annulation reactions.

Highly regio- and stereoselective synthesis of indene derivatives via electrophilic cyclization.

[reaction: see text] Indene or naphthalene derivatives are readily prepared in moderate to excellent yields with high regio- and stereoselectivity under very mild reaction conditions by the reaction of acetylenic malonates and ketones with I2, ICl, or NIS. The resulting iodides can be further elaborated using palladium-catalyzed coupling reactions.