Pentamethylcyclopentadienyl rhodium and iridium complexes containing oxinato ligands

Trinuclear Half‐Sandwich RuII, RhIII and IrIII Polyester Organometallic Complexes: Synthesis and in vitro Evaluation as Antitumor Agents

“…All complexes show that the metal centre adopts the so‐called “piano‐stool” geometry, with the metal coordinated to the pentamethylcyclopentadienyl or p ‐cymene ligand, one chloride ligand and N , N ‐ligand ( 5 and 6 ) or N , O ‐ligand ( 8 and 9 ). In 5 and 6 , the M–N distances follow the trends observed in other common N , N ‐coordinated metal complexes,28 while in 8 and 9 the M–N and N–O distances (Tables 1 and 2) are comparable to those observed in analogous rhodium and iridium (C 5 Me 5 ) complexes 29,30…”

Cp*CoIII‐Catalyzed Efficient Dehydrogenation of Secondary Alcohols

“…[13] The N1-Co-O1a ngle for five-membered metallacycle A is about 84.238,w hich is slightly larger as compared to reported N1-M-O1 angleso f7 8.408 (M = Rh) and 77.8 (M = Ir). [14] The CoÀOb ond and CoÀNb onds are 1.956 and 1.947 much shorter than those reported for RhÀO/ IrÀOb onds andR h ÀN/IrÀNb onds. [14] Thei solatedc omplex A shows the methyl protono ft he Cp* furtherh ighfield d = 1.61 ppm compared to Cp*Co(CO)I 2 for whicht he Cp* reso-nance appearsa td = 2.23 ppm.…”

“…[14] The CoÀOb ond and CoÀNb onds are 1.956 and 1.947 much shorter than those reported for RhÀO/ IrÀOb onds andR h ÀN/IrÀNb onds. [14] Thei solatedc omplex A shows the methyl protono ft he Cp* furtherh ighfield d = 1.61 ppm compared to Cp*Co(CO)I 2 for whicht he Cp* reso-nance appearsa td = 2.23 ppm. The crystal structure furtheri ndicatest hat the isolated cobalt complex A adopt 3-leg piano stool configuration.…”

“…To our delight, the ketone 2a was isolated in 66 %yield. Finally, we have performed the control experiments to realize the need of both cobalt catalyst and base, which results in no product formation (entry [13][14].…”

Arene ruthenium bis-saccharinato complexes: Synthesis, molecular structure and catalytic oxidation properties in aqueous solution

“…Based on an early observation by M. Baird [3], we found in the 1990s that chloride or tetrafluoroborate salts of cationic arene ruthenium complexes are well soluble in water, the arene ruthenium bond being robust towards hydrolysis [4e6], which resulted in a rapid development of arene ruthenium chemistry in aqueous solution [7]. Recently, we reported the synthesis of arene ruthenium oxinato complexes [(h 6 -arene)Ru(h 2 -N,O-L)(Cl)] and [(h 6 -arene)Ru(h 2 -N,O-L)(OH 2 )] þ , which catalyze the hydrogenation of carbon dioxide in aqueous solution in presence of KOH to give the formate, with catalytic turnovers up to 400 [8]. Saccharin, discovered by Remsen and Fahlberg in 1879, is about 500 times sweeter than sugar [9].…”