Search

Ru(BINAP)(PPh3)HCl cleanly reacts with LiCH2TMS to give Ru(BINAP)(PPh3) (1) that has been fully characterized, including by X‐ray diffraction (BINAP and TMS stand for (2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl and trimethylsilyl respectively). In sharp contrast with other carbonyl‐free phosphine complexes of Ru(0), 1 demonstrates a strikingly high thermal stability and no propensity for intramolecular C−H activation (cyclometalation). Yet 1 coordinates acetonitrile and readily exchanges its PPh3 ligand with alkenes and dienes, thus behaving like a "masked" 16‐e Ru(0) species. Electron‐poor alkenes coordinate more readily than electron‐rich ones, which testifies for the nucleophilic character of the Ru(0)‐BINAP fragment. While being thermally stable, 1 is highly reactive and is capable of activating C−H and N−H bonds, and even of cleaving an inert N−Et bond. The combination of high reactivity and stability originates from the P,arene‐chelation by the BINAP ligand, i.e., the coordinated π‐arene stabilizes Ru(0) to prevent cyclometalation, yet it can slide upon substrate coordination, thereby enabling a variety of inert bond activation reactions to occur under mild conditions. [ABSTRACT FROM AUTHOR]

Ru(BINAP)(PPh3)HCl cleanly reacts with LiCH2TMS to give Ru(BINAP)(PPh3) (1) that has been fully characterized, including by X‐ray diffraction (BINAP and TMS stand for (2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl and trimethylsilyl respectively). In sharp contrast with other carbonyl‐free phosphine complexes of Ru(0), 1 demonstrates a strikingly high thermal stability and no propensity for intramolecular C−H activation (cyclometalation). Yet 1 coordinates acetonitrile and readily exchanges its PPh3 ligand with alkenes and dienes, thus behaving like a "masked" 16‐e Ru(0) species. Electron‐poor alkenes coordinate more readily than electron‐rich ones, which testifies for the nucleophilic character of the Ru(0)‐BINAP fragment. While being thermally stable, 1 is highly reactive and is capable of activating C−H and N−H bonds, and even of cleaving an inert N−Et bond. The combination of high reactivity and stability originates from the P,arene‐chelation by the BINAP ligand, i.e., the coordinated π‐arene stabilizes Ru(0) to prevent cyclometalation, yet it can slide upon substrate coordination, thereby enabling a variety of inert bond activation reactions to occur under mild conditions. [ABSTRACT FROM AUTHOR]

Ru(BINAP)(PPh3)HCl cleanly reacts with LiCH2TMS to give Ru(BINAP)(PPh3) (1) that has been fully characterized, including by X‐ray diffraction (BINAP and TMS stand for (2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl and trimethylsilyl respectively). In sharp contrast with other carbonyl‐free phosphine complexes of Ru(0), 1 demonstrates a strikingly high thermal stability and no propensity for intramolecular C−H activation (cyclometalation). Yet 1 coordinates acetonitrile and readily exchanges its PPh3 ligand with alkenes and dienes, thus behaving like a "masked" 16‐e Ru(0) species. Electron‐poor alkenes coordinate more readily than electron‐rich ones, which testifies for the nucleophilic character of the Ru(0)‐BINAP fragment. While being thermally stable, 1 is highly reactive and is capable of activating C−H and N−H bonds, and even of cleaving an inert N−Et bond. The combination of high reactivity and stability originates from the P,arene‐chelation by the BINAP ligand, i.e., the coordinated π‐arene stabilizes Ru(0) to prevent cyclometalation, yet it can slide upon substrate coordination, thereby enabling a variety of inert bond activation reactions to occur under mild conditions. [ABSTRACT FROM AUTHOR]

Ru(BINAP)(PPh3)HCl cleanly reacts with LiCH2TMS to give Ru(BINAP)(PPh3) (1) that has been fully characterized, including by X‐ray diffraction (BINAP and TMS stand for (2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl and trimethylsilyl respectively). In sharp contrast with other carbonyl‐free phosphine complexes of Ru(0), 1 demonstrates a strikingly high thermal stability and no propensity for intramolecular C−H activation (cyclometalation). Yet 1 coordinates acetonitrile and readily exchanges its PPh3 ligand with alkenes and dienes, thus behaving like a "masked" 16‐e Ru(0) species. Electron‐poor alkenes coordinate more readily than electron‐rich ones, which testifies for the nucleophilic character of the Ru(0)‐BINAP fragment. While being thermally stable, 1 is highly reactive and is capable of activating C−H and N−H bonds, and even of cleaving an inert N−Et bond. The combination of high reactivity and stability originates from the P,arene‐chelation by the BINAP ligand, i.e., the coordinated π‐arene stabilizes Ru(0) to prevent cyclometalation, yet it can slide upon substrate coordination, thereby enabling a variety of inert bond activation reactions to occur under mild conditions. [ABSTRACT FROM AUTHOR]

Luminescent cuprous complexes are an important class of coordination compounds due to their relative abundance, low cost and ability to display excellent luminescence. The title heteroleptic cuprous complex, [2,2′‐bis(diphenylphosphanyl)‐1,1′‐binaphthyl‐κ2P,P′](2‐phenylpyridine‐κN)copper(I) hexafluoridophosphate, rac‐[Cu(C44H32P2)(C11H9N)]PF6, conventionally abbreviated rac‐[Cu(BINAP)(2‐PhPy)]PF6 (I), where BINAP and 2‐PhPy represent 2,2′‐bis(diphenylphosphanyl)‐1,1′‐binaphthyl and 2‐phenylpyridine, respectively, is described. In this complex, the asymmetric unit consists of a hexafluoridophosphate anion and a heteroleptic cuprous complex cation, in which the cuprous centre in a CuP2N coordination triangle is coordinated by two P atoms from the BINAP ligand and by one N atom from the 2‐PhPy ligand. Time‐dependent density functional theory (TD–DFT) calculations show that the UV–Vis absorption of I should be attributed to ligand‐to‐ligand charge transfer (LLCT) characteristic excited states. It was also found that the paper‐based film of this complex exhibited obvious luminescence light‐up sensing for pyridine. [ABSTRACT FROM AUTHOR]

Herein, we disclosed the contra‐thermodynamic E→Z isomerization of alkenyl silanes, according to the in situ formation of a chromophoric species, in the presence of rac‐BINAP as the catalyst. The reaction carried out in DMSO or CH3CN under irradiation at 405 nm allowed the interconversion of the E‐isomers into the Z‐congeners in good to excellent yields and outstanding Z/E selectivities, on 18 examples. Finally, the mechanism of this E→Z isomerization was studied to get insight into the reaction mechanism. [ABSTRACT FROM AUTHOR]

A series of novel 'drug-like' small molecules based on 1 H -benzo[ d ]imidazole derivatives bearing furan-2-yl, 4-piperidine and 5-aryl/aminoaryl substitutions were designed and synthesised. The key intermediate tert -butyl-4-(5-bromo-2-(furan-2-yl)-1 H -benzo[ d ]imidazol-1-yl)piperidine-1-carboxylate (5) was synthesised via sequential reaction starting from 4-bromo-1-fluoro-2-nitrobenzene (1). The 5-aryl-substituted molecular library was generated via Suzuki–Miyura coupling of tert -butyl-4-(5-bromo-2-(furan-2-yl)-1 H -benzo[ d ]imidazol-1-yl)piperidine-1-carboxylate (5) with various boronic acids while Buchwald coupling of 5 with various anilines generated the second molecular library of tert -butyl-4-(2-(furan-2-yl)-5-(arylamino)-1 H -benzo[ d ]imidazol-1-yl)piperidine-1-carboxylates. The structures of all the newly synthesised compounds were confirmed by spectral analysis. The optimised procedure gives easy access to two new molecular libraries of 1 H -benzo[ d ]imidazoles with operational simplicity and good yield. A series of novel 'drug-like' small molecules based on 1 H -benzo[ d ]imidazole derivatives bearing furan-2-yl, 4-piperidine and 5-aryl/aminoaryl substitutions were designed and synthesised. The optimised procedure gave easy access to two novel molecular libraries of 1 H -benzo[ d ]imidazoles with operational simplicity and good yield. [ABSTRACT FROM AUTHOR]

Ru(BINAP)(PPh 3 )HCl cleanly reacts with LiCH 2 TMS to give Ru(BINAP)(PPh 3 ) (1) that has been fully characterized, including by X-ray diffraction (BINAP and TMS stand for (2,2'-bis(diphenylphosphino)-1,1'-binaphthyl and trimethylsilyl respectively). In sharp contrast with other carbonyl-free phosphine complexes of Ru(0), 1 demonstrates a strikingly high thermal stability and no propensity for intramolecular C-H activation (cyclometalation). Yet 1 coordinates acetonitrile and readily exchanges its PPh 3 ligand with alkenes and dienes, thus behaving like a "masked" 16-e Ru(0) species. Electron-poor alkenes coordinate more readily than electron-rich ones, which testifies for the nucleophilic character of the Ru(0)-BINAP fragment. While being thermally stable, 1 is highly reactive and is capable of activating C-H and N-H bonds, and even of cleaving an inert N-Et bond. The combination of high reactivity and stability originates from the P,arene-chelation by the BINAP ligand, i.e., the coordinated π-arene stabilizes Ru(0) to prevent cyclometalation, yet it can slide upon substrate coordination, thereby enabling a variety of inert bond activation reactions to occur under mild conditions., (© 2024 The Authors. Published by Wiley-VCH GmbH.)

Asymmetric catalysis is the preferred method for the synthesis of pure chiral molecules in the fine chemical industry. Cellulose has long been sought as a support in enantioselective catalysis. Dialdehyde cellulose (DAC) is produced by the selective oxidation of cellulose and is used to bind 5,5′-diamino Binap by forming a Schiff base. Here, we report the synthesis of modified cellulose-supported Rh as a novel biomass-supported catalyst and the characterization of its morphology, composition, and thermal stability. DAC-BINAP-Rh was a very effective catalyst in the asymmetric hydrogenation of enamides and could be easily recycled. This work provides a novel supported catalyst that broadens the applications of cellulose in asymmetric catalysis.

Luminescent cuprous complexes are an important class of coordination compounds due to their relative abundance, low cost and ability to display excellent luminescence. The title heteroleptic cuprous complex, [2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl-κ 2 P,P'](2-phenylpyridine-κN)copper(I) hexafluoridophosphate, rac-[Cu(C 44 H 32 P 2 )(C 11 H 9 N)]PF 6 , conventionally abbreviated rac-[Cu(BINAP)(2-PhPy)]PF 6 (I), where BINAP and 2-PhPy represent 2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl and 2-phenylpyridine, respectively, is described. In this complex, the asymmetric unit consists of a hexafluoridophosphate anion and a heteroleptic cuprous complex cation, in which the cuprous centre in a CuP 2 N coordination triangle is coordinated by two P atoms from the BINAP ligand and by one N atom from the 2-PhPy ligand. Time-dependent density functional theory (TD-DFT) calculations show that the UV-Vis absorption of I should be attributed to ligand-to-ligand charge transfer (LLCT) characteristic excited states. It was also found that the paper-based film of this complex exhibited obvious luminescence light-up sensing for pyridine.

Asymmetric catalysis is the preferred method for the synthesis of pure chiral molecules in the fine chemical industry. Cellulose has long been sought as a support in enantioselective catalysis. Dialdehyde cellulose (DAC) is produced by the selective oxidation of cellulose and is used to bind 5,5′-diamino Binap by forming a Schiff base. Here, we report the synthesis of modified cellulose-supported Rh as a novel biomass-supported catalyst and the characterization of its morphology, composition, and thermal stability. DAC-BINAP-Rh was a very effective catalyst in the asymmetric hydrogenation of enamides and could be easily recycled. This work provides a novel supported catalyst that broadens the applications of cellulose in asymmetric catalysis. [ABSTRACT FROM AUTHOR]

[Display omitted] Herein reported is the convenient and efficient strategy for the preparation of binaphthyl-based phosphines through direct modification to the commercially available 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) with sodium. In the absence of 15-crown-5-ether, a cyclic sodium dinapthylphospholide intermediate is mainly generated. With 15-crown-5-ether, P-Ph bonds are selectively cleft by Na to produce binaphthyl-based disodium phosphides. The mechanism of selective formation of sodium dinapthylphospholide or binaphthyl-based disodium phosphides is proposed. [ABSTRACT FROM AUTHOR]