71-47-6Relevant articles and documents
Flowing afterglow study of the gas phase nucleophilic reactions of some formyl, acetyl and cyclic esters
Frink, Brian T.,Hadad, Christopher M.
, p. 2397 - 2407 (1999)
A variety of nucleophiles have been investigated for their reactions with formyl and acetyl esters in the gas phase in our flowing afterglow. The reactions that are permitted in the gas phase are more varied than those seen in the condensed phase. The rates of reactions of methyl and ethyl esters as well as various lactones have been undertaken with various nucleophiles: H2N-, HO-, CH3O, NCCH2-, F-, CH3C(=O)CH2-, CH3S- and O2NCH2-. For example, the reaction rate of NCCH2- + HCO2CH2CH3 has been found to be (1.3 ± 0.2) x 10-10 cm3 molecule-1 s-1 and the only product is HC(O-)=CHCN which results from nucleophilic acyl substitution (BAC2) followed by a proton transfer within the ion-molecule complex. Other reaction mechanisms that have been observed include β-elimination (E2), bimolecular nucleophilic substitution at the alkyl group (BAL2), and the Riveros reaction (elimination of CO). A mechanism for the F- + HCO2CH3 reaction has been determined at the B3LYP/6-31 + G(d) level. Most notably, channels were determined computationally (6AL2 and Riveros), and these channels are also observed experimentally. Furthermore, the BAC2 pathway which proceeds via nucleophilic attack on the carbonyl group also leads to the Riveros products, F-(CH3OH) and CO.
Symmetry-Broken Au–Cu Heterostructures and their Tandem Catalysis Process in Electrochemical CO2 Reduction
Jia, Henglei,Yang, Yuanyuan,Chow, Tsz Him,Zhang, Han,Liu, Xiyue,Wang, Jianfang,Zhang, Chun-yang
, (2021/04/27)
Symmetry-breaking synthesis of colloidal nanocrystals with desired structures and properties has aroused widespread interest in various fields, but the lack of robust synthetic protocols and the complex growth kinetics limit their practical applications. Herein, a general strategy is developed to synthesize the Au–Cu Janus nanocrystals (JNCs) through the site-selective growth of Cu nanodomains on Au nanocrystals, which is directed by the substantial lattice mismatch between them, with the assistance of judicious manipulation of the growth kinetics. This strategy can work on Au nanocrystals with different architectures for the achievement of diverse asymmetric Au–Cu hybrid nanostructures. Of particular note, the obtained Au nanobipyramids (Au NBPs)-based JNCs facilitate the conversion of CO2 to C2 hydrocarbon production during electrocatalysis, with the Faradaic efficiency and maximum partial current density being 4.1-fold and 6.4-fold higher than those of their monometallic Cu counterparts, respectively. The excellent electrocatalytic performances benefit from the special design of the Au–Cu Janus architectures and their tandem catalysis mechanism as well as the high-index facets on Au nanocrystals. This research provides a new approach to synthesize various hybrid Janus nanostructures, facilitating the study of structure-function relationship in the catalytic process and the rational design of efficient heterogeneous electrocatalysts.
Erratum: Thermodynamic Analysis of Metal-Ligand Cooperativity of PNP Ru Complexes: Implications for CO2Hydrogenation to Methanol and Catalyst Inhibition (J. Am. Chem. Soc. (2019) 141:36 (14317-14328) DOI: 10.1021/jacs.9b06760)
Ardon, Yotam,Geary, Jackson,Mathis, Cheryl L.,Philliber, Mallory A.,Reese, Maxwell S.,Saouma, Caroline T.,Vanderlinden, Ryan T.
supporting information, p. 11274 - 11274 (2021/08/03)
Equation 13 in the Supporting Information contained a sign error, resulting in the incorrect pKa values reported for (PNP)Ru-CO2and PNP. The pKa of (PNP)Ru-CO2should be 26.1 ± 0.4 (not 24.6 ± 0.4). The pKa of PNP should be 29.0 ± 0.4 (not 28.6 ± 0.4). The same incorrect pKa values are reported on page 14322, in the left column, last paragraph for PNP, and in the right column, first paragraph for (PNP)Ru-CO2), and on page 14323, in Table 2, as well as in the SI (Table S3 and Figure S12 caption). Also in the Supporting Information, Figures S15 and S17 have the wrong functions plotted. The slope of the correct function was used in extrapolating thermochemical parameters derived from Figure S17. The slope of Figure S15 was used to extrapolate thermochemical parameters, which resulted in our reporting incorrect values. The value of K8,Cl should be 0.004 ± 0.0016 (not 2.5 × 10-7). The value of K5,Cl should be 2.0(±0.8) × 10-31(not 1.3 × 10-34), and hence the corresponding pKa should be >29.7 ± 0.2 (not >33.9 ± 0.4). The value of K6,Clshould be 1.0(±0.6) × 10-7(not 6.3 × 10-12), and hence the corresponding ΔG6,Cl should be 9.5 ± 0.3 kcalmol-1(not 15.3 ± 0.5 kcalmol-1). A corrected Supporting Information file is provided that has revised versions of eq 13, Figure S12 caption, Figure S15, Figure S17, and Table S3. The corrected Table 2 is shown below. None of these errors impact the discussion and conclusions drawn. We regret these errors and apologize for any confusion that may have resulted.
