Journal of Structural Chemistry, Год журнала: 2021, Номер 62(7), С. 1056 - 1065
Опубликована: Июль 1, 2021
Язык: Английский
Journal of Structural Chemistry, Год журнала: 2021, Номер 62(7), С. 1056 - 1065
Опубликована: Июль 1, 2021
Язык: Английский
Catalysts, Год журнала: 2020, Номер 10(2), С. 162 - 162
Опубликована: Фев. 1, 2020
The reduction of ketones through homogeneous transfer hydrogenation catalyzed by transition metals is one the most important routes for obtaining alcohols from carbonyl compounds. interest this method increases when opportune catalytic precursors are able to perform transformation in an asymmetric fashion, generating enantiomerically enriched chiral alcohols. This reaction has been extensively studied terms catalysts and variety substrates. A large amount information about possible mechanisms available nowadays, which high importance development systems with excellent outcomes conversion, enantioselectivity Turn Over Frequency. On other side, many mechanistic aspects still unclear, especially those have shown only moderate performances hydeogenation. case neutral [RuCl2(η6-arene)(P)] cationic [Rh(PP)2]X (X = anion; P PP mono- bidentate phosphine, respectively) complexes. Herein, a summary known Transfer Hydrogenation these complexes provided continuous focus on more relevant features.
Язык: Английский
Процитировано
19Dalton Transactions, Год журнала: 2019, Номер 48(33), С. 12560 - 12576
Опубликована: Янв. 1, 2019
A series of novel monocarbonyl ruthenium catalysts containing bidentate dinitrogen or/and diphosphine ligands are easily obtained through a general and straightforward approach.
Язык: Английский
Процитировано
16ChemCatChem, Год журнала: 2020, Номер 12(13), С. 3537 - 3544
Опубликована: Апрель 18, 2020
Abstract The mixed acetate acetylacetonate (acac) ruthenium(II) phosphine complexes Ru(OAc)(acac)P 2 [P =(PPh 3 ) , Ph P(CH 4 PPh (dppb)] were prepared by protonation of Ru(OAc) (PPh with acetylacetone in dichloromethane. Reaction the dppb derivative 2‐(aminomethyl)pyridine (ampy) affords complex Ru(OAc)(acac)(ampy)(dppb), which converts to [Ru(acac)(ampy)(dppb)](OAc) toluene at 90 °C. In former ampy ligand is monodentate and coordinates through NH ‐moiety. isolated acac are active catalysts for transfer hydrogenation ketones loadings as low 0.01 mol%, having a strong accelerating effect. Several aromatic aliphatic ketone substrates converted their corresponding alcohols, different electronic influences substituents on acetophenone tolerated.
Язык: Английский
Процитировано
13Dalton Transactions, Год журнала: 2020, Номер 49(24), С. 8375 - 8388
Опубликована: Янв. 1, 2020
High cytotoxic and antimetastatic activities against anaplastic thyroid cancer are displayed by cationic complexes [RuX(CO)(dppb)(phen)]Y (X = Y OAc, OPiv, SAc, NCS; X Cl PF6).
Язык: Английский
Процитировано
13Catalysis Science & Technology, Год журнала: 2022, Номер 12(18), С. 5597 - 5603
Опубликована: Янв. 1, 2022
Preparation of bis-aNHC Ru catalysts, identification formation intermediates and application in transfer hydrogenation Oppenauer-type oxidation, observing an inversion activity appearing to be dependent on steric hindrance.
Язык: Английский
Процитировано
9Organometallics, Год журнала: 2021, Номер 40(8), С. 1086 - 1103
Опубликована: Апрель 14, 2021
The diacetate complexes trans-[Ru(κ1-OAc)2(PPh3)2(NN)] (NN = ethylenediamine (en) (1), 2-(aminomethyl)pyridine (ampy) (2), 2-(aminomethyl)pyrimidine (ampyrim) (3)) have been isolated in 76–88% yield by reaction of [Ru(κ2-OAc)2(PPh3)2] with the corresponding nitrogen ligands. ampy-type derivatives 2 and 3 undergo isomerization to thermodynamically most stable cationic [Ru(κ1-OAc)(PPh3)2(NN)]OAc (2a 3a) cis-[Ru(κ1-OAc)2(PPh3)2(NN)] (2b 3b) methanol at RT. trans-[Ru(κ1-OAc)2(P2)2] (P2 dppm (4), dppe (5)) compounds synthesized from suitable diphosphine toluene 95 °C. complex cis-[Ru(κ1-OAc)2(dppm)(ampy)](6) has obtained reflux ampy. trans-[Ru(κ1-OAc)2P2(NN)] (7–16; NN en, ampy, ampyrim, 8-aminoquinoline; P2 dppp, dppb, dppf, (R)-BINAP) can be easily a treatment ligands Alternatively these prepared trans-[Ru(OAc)2(PPh3)2(NN)] MEK 50 use (R)-BINAP affords trans-[Ru(κ1-OAc)2((R)-BINAP)(NN)] ampy (11), ampyrim (15)) as single stereoisomers. Treatment 8–15 RT leads [Ru(κ2-OAc)P2(NN)]OAc (8a–15a; ampyrim; (R)-BINAP). Similarly 2, dipivalate trans-[Ru(κ1-OPiv)2(PPh3)2(ampy)] (18) is [Ru(κ2-OPiv)2(PPh3)2] (17) CHCl3. pincer acetate [Ru(κ1-OAc)(CNNOMe)(PPh3)2] (19) HCNNOMe ligand 2-propanol NEt3 reflux. In addition, dppb [Ru(κ1-OAc)(CNN)(dppb)] (CNN AMTP (20), AMBQPh (21)) [Ru(κ2-OAc)2(PPh3)2], HAMTP or HAMBQPh NEt3, respectively. are active transfer hydrogenation H2 carbonyl S/C values up 10000 TOF 160000 h–1.
Язык: Английский
Процитировано
9Organometallics, Год журнала: 2020, Номер 39(17), С. 3180 - 3193
Опубликована: Авг. 18, 2020
Several mononuclear ruthenium complexes containing bulky diphosphines have been easily prepared from acetate precursors. The cyclohexyl complex [Ru(η2-OAc)2(DCyPF)] (1-cy; DCyPF = 1,1′-bis(dicyclohexylphosphino)ferrocene) is synthesized [Ru(η2-OAc)2(PPh3)2] and in toluene at reflux, whereas the ethylenediamine (en) derivatives trans-[Ru(η1-OAc)2(PP)(en)] (PP 1,1′-bis(diisopropylphosphino)ferrocene (DiPPF) (2), (3)) obtained a one-pot reaction [Ru(η2-OAc)2(PPh3)2], PP, en n-heptane. Treatment of isopropylphosphine [Ru(η2-OAc)2(DiPPF)] (1-ip) with 2-(aminomethyl)pyridine (ampy) methanol affords isolation mixture cationic [Ru(η2-OAc)(DiPPF)(ampy)]OAc (5a) cis-[Ru(η1-OAc)2(DiPPF)(ampy)] (5b) (4/1 molar ratio), via trans-[Ru(η1-OAc)2(DiPPF)(ampy)] (4) characterized low temperature. analogous compound trans-[Ru(η1-OAc)2(DCyPF)(ampy)] (6), ampy heptane, slowly converts into [Ru(η2-OAc)(DCyPF)(ampy)]OAc (7) RT. monocarbonyl [Ru(η1-OAc)(η2-OAc)(PP)(CO)] 1,3-bis(cyclohexylphosphino)propane (DCyPP) (8), (R)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyldicyclohexylphosphine (Josiphoscy) (9)) are [Ru(η1-OAc)(η2-OAc)(PPh3)2(CO)] suitable diphosphine. [Ru(η1-OAc)(η2-OAc)(DiPPF)(CO)] (10) phenylacetylene presence pyridine leads to alkynyl [Ru(η2-OAc)(C≡CPh)(DiPPF)(CO)] (11), by X-ray diffraction analysis. Protonation 10 2 equiv TFA RT gives [Ru(η1-OCOCF3)(η2-OCOCF3)(DiPPF)(CO)] (12). dicarbonyl trans,cis-[Ru(η1-OAc)2(DiPPF)(CO)2] (13) 1-ip CO (1 atm) CH2Cl2, isomer cis,cis-[Ru(η1-OAc)2(DiPPF)(CO)2] (14) can be carbonylation 10. When 13 heated solid state, formed decarbonylation. These promote transfer hydrogenation acetophenone 2-propanol (S/C 1000–2000) NaOiPr (2 mol %), affording TOF value up 81000 h–1 for 9 30 °C. Complex catalyzes head-to-head dimerization terminal alkynes 1,4-enynes reflux high stereoselectivity kinetic Z isomer.
Язык: Английский
Процитировано
8Inorganic Chemistry Communications, Год журнала: 2020, Номер 119, С. 108064 - 108064
Опубликована: Июнь 29, 2020
Язык: Английский
Процитировано
4Processes, Год журнала: 2024, Номер 12(7), С. 1413 - 1413
Опубликована: Июль 6, 2024
Recently, scientists have been developing sustainable processes, and in this context, mechanochemistry is commonly associated with green chemistry for its ability to reduce waste generation from chemical reactions. The well-known acetate complex, diacetate bis(triphenylphosphine) ruthenium(II) [Ru(OAc)2(PPh3)2], a versatile precursor preparing active complexes several catalytic This report presents an efficient straightforward manual grinding protocol the synthesis of ruthenium carboxylate starting commercially available [RuCl2(PPh3)3] metal carboxylates. work represents novel preliminary investigation into precursors’ alternative solventless route based on grinding. To our knowledge, first time [Ru(OAc)2(PPh3)2] has prepared via mechanochemical procedure. method also investigated other alkali carboxylates yields ranging 30 80% were obtained. A comparison sustainability environmental impact between conventional solution carried out using E-factor Mass Productivity. While complex MP only slightly better compared solvent (3 vs. 4 ~6 5 MP), benzoate higher results found (1 ~4 10 MP).
Язык: Английский
Процитировано
0Elsevier eBooks, Год журнала: 2022, Номер unknown, С. 444 - 527
Опубликована: Янв. 1, 2022
Язык: Английский
Процитировано
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