590-29-4Relevant articles and documents
Catalytic hydrogenation of carbon dioxide using Ir(III)-pincer complexes
Tanaka, Ryo,Yamashita, Makoto,Nozaki, Kyoko
, p. 14168 - 14169 (2009)
(Chemical Equation Presented) Catalytic hydrogenation of carbon dioxide in aqueous potassium hydroxide was performed using a newly synthesized isopropyl-substituted PNP-pincer iridium trihydride complex as a catalyst. Potassium formate was obtained with t
Heavy-atom isotope effects on the alkaline hydrolysis of methyl formate: The role of hydroxide ion in ester hydrolysis
Marlier, John F.
, p. 5953 - 5956 (1993)
Carbonyl carbon, carbonyl oxygen, and nucleophile oxygen isotope effects were measured for the alkaline hydrolysis of methyl formate in water at 25 °C. The carbonyl carbon isotope effect is k12/k13 = 1.0338, the isotope effect for the carbonyl oxygen is k16/k18 = 0.999, and that for the oxygen nucleophile is k16/k18 = 1.023. These isotope effects are consistent with a stepwise mechanism in which the formation of the tetrahedral intermediate is largely rate-determining. The isotope effect on the oxygen nucleophile suggests that the attacking nucleophile in aqueous alkali is water with general base assistance from hydroxide.
Arene ruthenium oxinato complexes: Synthesis, molecular structure and catalytic activity for the hydrogenation of carbon dioxide in aqueous solution
Thai, Trieu-Tien,Therrien, Bruno,Süss-Fink, Georg
, p. 3973 - 3981 (2009)
Two families of arene ruthenium oxinato complexes of the types [(η6-arene)Ru(η2-N,O-L)Cl] and [(η6-arene)Ru(η2-N,O-L)(OH2)]+ have been synthesized from the dinuclear precursors [(η6/s
Hydrogenation of CO2 to Formate with H2: Transition Metal Free Catalyst Based on a Lewis Pair
Zhao, Tianxiang,Hu, Xingbang,Wu, Youting,Zhang, Zhibing
, p. 722 - 726 (2019)
Hydrogenation of CO2 to formate with H2 in the absence of transition metal is a long-standing challenge in catalysis. The reactions between tris(pentafluorophenyl)borane (BCF) and K2CO3 (or KHCO3) are found to form a Lewis pair (K2[(BCF)2?CO3]) which can react with both H2 and CO2 to produce formate. Based on these stoichiometric reactions, the first catalytic hydrogenation process of CO2 to formate using transition metal free catalyst (BCF/M2CO3, M=Na, K, and Cs) is reported. The highest TON value of this catalytic process is up to 3941. Further research revealed the reaction mechanism in which the Lewis pair enables the splitting of H2 and the insertion of CO2 into the B?H bond.
Synthetic routes to a coordinatively unsaturated ruthenium complex supported by a tripodal, protic bis(N-heterocyclic carbene) phosphine ligand
Flowers,Johnson,Pitre,Cossairt
, p. 1276 - 1283 (2018)
A facile, one pot synthesis of a coordinatively unsaturated ruthenium complex supported by a tripodal, protic bis(N-heterocyclic carbene) phosphine ligand is presented. A number of coordination complexes were discovered en route during this synthesis, revealing some of the unique aspects of complexes ligated by this type of tridentate, protic bis(NHC) ligand. Through a combination of 1D and 2D NMR spectroscopic analysis and single crystal X-ray diffraction, we reveal the intermediacy of phosphine-ligated bisimidazole complexes and show that abstraction of inner-sphere halide ions facilitates conversion to the desired tridentate bis(NHC) coordination mode. Ultimately the use of N-methyl-2-pyrrolidone is shown to enable the use of the extreme temperatures needed to facilitate the direct, thermally activated tautomerization reaction that gives rise to the bis(NHC) motif.
Highly efficient hydrogenation of carbon dioxide to formate catalyzed by iridium(iii) complexes of imine-diphosphine ligands
Liu, Chong,Xie, Jian-Hua,Tian, Gui-Long,Li, Wei,Zhou, Qi-Lin
, p. 2928 - 2931 (2015)
A new iridium catalyst containing an imine-diphosphine ligand has been developed, which showed high efficiency for the hydrogenation of CO2 to formate (yield up to 99%, TON up to 450000). A possible catalytic mechanism is proposed, in which the imine group of the catalyst plays a key role in the cleavage of H2 and the activation of CO2.
Enhanced CO2 electroreduction efficiency through secondary coordination effects on a pincer iridium catalyst
Ahn, Steven T.,Bielinski, Elizabeth A.,Lane, Elizabeth M.,Chen, Yanqiao,Bernskoetter, Wesley H.,Hazari, Nilay,Palmore, G. Tayhas R.
, p. 5947 - 5950 (2015)
An iridium(iii) trihydride complex supported by a pincer ligand with a hydrogen bond donor in the secondary coordination sphere promotes the electrocatalytic reduction of CO2 to formate in water/acetonitrile with excellent Faradaic efficiency and low overpotential. Preliminary mechanistic experiments indicate formate formation is facile while product release is a kinetically difficult step.
Cobalt-Catalyzed Synthesis of Unsymmetrically N, N-Disubstituted Formamides via Reductive Coupling of Primary Amines and Aldehydes with CO2 and H2
Ke, Zhengang,Yang, Zhenzhen,Liu, Zhenghui,Yu, Bo,Zhao, Yanfei,Guo, Shien,Wu, Yunyan,Liu, Zhimin
, p. 6622 - 6626 (2018)
Herein, a novel route to synthesize unsymmetrically N,N-disubstituted formamides is reported, which is achieved via reductive coupling of primary amine and aldehyde with CO2/H2 over a cobalt-based catalytic system composed of CoF2, P(CH2CH2PPh2)3 and K2CO3. The mechanism investigation indicates that a secondary amine is formed via hydrogenation of the imine originated from aldehyde and primary amine, which further reacts with HCOOH generated from CO2 hydrogenation, resulting in the formation of NNFA finally.
Transfer hydrogenation of carbon dioxide: Via bicarbonate promoted by bifunctional C-N chelating Cp?Ir complexes
Sato, Yasuhiro,Kayaki, Yoshihito,Ikariya, Takao
, p. 10762 - 10765 (2020)
Metal-ligand cooperative Cp?Ir(iii) complexes derived from primary benzylic amines effectively promote transfer hydrogenation of atmospheric CO2 using 2-propanol at 80 °C. Isotope-labelling experiments strengthen that active Ir species can preferentially reduce bicarbonate congeners formed from CO2. The powerful transfer hydrogenation catalyst exhibits remarkable activity for the conversion of bicarbonates into formate salts with a turnover number up to 3200, even without H2 and CO2.
CO2Hydrogenation Catalyzed by a Ruthenium Protic N-Heterocyclic Carbene Complex
Johnson, M. Cecilia,Rogers, Dylan,Kaminsky, Werner,Cossairt, Brandi M.
, p. 5996 - 6003 (2021)
We describe the hydrogenation of CO2 to formate catalyzed by a Ru(II) bis(protic N-heterocyclic carbene, p-NHC) phosphine complex [Ru(bpy)(MeCN)(PPh(p-NHC)2)](PF6)2 (1). Under catalytic conditions (20 μmol catalyst, 20 bar CO2, 60 bar H2, 5 mL THF, 140 °C, 16 h), the activity of 1 is limited only by the amount of K3PO4 present in the reaction, yielding a nearly 1:1 ratio of turnover number (TON) to equivalents of K3PO4 (relative to 1), with the highest TON = 8040. Additionally, analysis of the reaction solution post-run reveals the catalyst intact with no free ligand observed. Stoichiometric studies, including examination of unique carbamate and hydride complexes as relevant intermediates, were carried out to probe the operative mechanism and understand the importance of metal-ligand cooperativity in this system.
