35733-58-5Relevant articles and documents
Mapping the Intricate Reactivity of Nanojars toward Molecules of Varying Acidity and Their Conjugate Bases Leading to Exchange of Pyrazolate Ligands
Hartman, Christian K.,Mezei, Gellert
, p. 10609 - 10624 (2017)
A comprehensive reactivity study of nanojars toward 18 different acidic compounds with varying pKa, including 12 different carboxylic acids (both aliphatic and aromatic mono- and dicarboxylic acids), p-toluenesulfonic acid, hydrogen sulfate, hydrogen carbonate, carbonic acid, 1-decanethiol, and methanol, as well as four different conjugate bases (formate, acetate, benzoate, 2-bromoethanesulfonate) is carried out with the aid of electrospray-ionization mass spectrometry. Thus, the effect on nanojar substitution and breakdown pattern of a number of variables, such as concentration of reagent (acid or conjugate base), acidity of reagent (pKa), effect of acid vs conjugate base, steric effects, aromaticity, incarcerated anion and size of the nanojar, is evaluated. Of the substitution and breakdown products identified by mass spectrometry, acetate-substituted nanojars (Bu4N)2[CO3?{Cu27(μ-OH)27(μ-pz)27-x(μ-CH3COO)x}] (x = 1 and 2), as well as dimeric complexes (Bu4N)2[Cu2(μ-pz)2A2] (A = CO32- and SO42-) have been isolated and characterized by single-crystal X-ray diffraction. This study offers a detailed understanding of the behavior of nanojars of various sizes and with different incarcerated anions in the presence of the above-mentioned compounds at varying concentrations and tests the limits of the pyrazolate/carboxylate structural analogy in multinuclear metal complexes. The results point to the possibility of obtaining functionalized nanojars via pyrazolate/carboxylate ligand exchange, an aid in the design of anion extraction processes using nanojars or similar complexes as extracting agents.
Synthesis of silyl formates, formamides, and aldehydesviasolvent-free organocatalytic hydrosilylation of CO2
Ema, Tadashi,Hasegawa, Jun-Ya,Hiyoshi, Mahoko,Murata, Takumi,Ratanasak, Manussada
supporting information, p. 5783 - 5786 (2020/06/03)
Carbon dioxide (CO2) was used as a C1 source to prepare silyl formates, formamides, and aldehydes. Tetrabutylammonium acetate (TBAA) catalyzed the solvent-freeN-formylation of amines with CO2and hydrosilane to give formamides including Weinreb formamide, Me(MeO)NCHO, which was successively converted into aldehydes by one-pot reactions with Grignard reagents.
Use of formate salts as a hydride and a Co2 source in PGeP -palladium complex-catalyzed hydrocarboxylation of allenes
Zhu, Chuan,Takaya, Jun,Iwasawa, Nobuharu
supporting information, p. 1814 - 1817 (2015/04/14)
Use of formate salts as a hydride as well as a CO2 source was achieved in a PGeP-palladium complex-catalyzed hydrocarboxylation of allenes through a highly efficient decarboxylation-carboxylation process. This reaction proceeds under mild conditions and provides an alternative strategy for utilizing formate salts as a C1 source.