Chemical Decomposition of the TFSI Anion Under Aqueous Basic Conditions

Understanding the interfacial reactivity of aqueous electrolytes is crucial for their use in future batteries. We investigate the reactivity of the bis(trifluoromethane)sulfonimide (TFSI) anion when exposed to a strong alkaline medium, by means of ab initio molecular dynamics and enhanced sampling techniques. In particular, we study the nucleophilic attack by the hydroxide anion, which was proposed as a mechanism for the formation of the solid electrolyte interphase at the negative electrode with water-in-salt electrolytes. While in the gas phase we recover a stable gaseous product, namely fluoroform, we observe the formation of trifluoromethanol in strong basic conditions, which then rapidly deprotonates to form CF3O-. This anion was suggested recently as a key compound leading to the formation of a solid electrolyte interphase on an Si-C anode. Such an approach could be leveraged to discover convenient additives leading to the formation of a stable interphase.

On the photochemical reaction of pyridinium salts with nucleophiles

DFT calculations on the photochemical reaction of 1-n–N-butylpyridinium salt in water with hydroxide anion is in agreement with a singlet state process where the S2 state at λ = 253 nm can be converted into a Dewar isomer (2-butyl-2-azabicyclo[2.2.0]hexa-2,5-dien-2-yl cation). The Dewar isomer can react with hydroxide anion giving the product, 6-n-butyl-6-azabicyclo[3.1.0]hex-3-en-2-ol.

Automated reaction mechanisms and kinetics based transition state search process AMK-gau_xtb and its application to the substitution reaction of the nitroso group in 2,4,6-trinitrotoluene by hydroxide anion in the aqueous phase

The newly developed AMK-gau_xtb discovers new TNT alkaline hydrolysis mechanism characteristics.

4-Cyano-3-oxotetrahydrothiophene (c-THT): An Ideal Acrylonitrile Anion Equivalent

Abstract4-Cyano-3-oxotetrahydrothiophene (c-THT) has much more to offer than just a platform to various heterocyclic scaffolds. This solid, bench-stable and commercially available reagent can be readily transformed into thioglycolic acid and acrylonitrile upon simple addition of a hydroxide anion. This interesting feature enables its use as a particularly versatile acrylonitrile anion surrogate.

Converting Mn/Al layered double hydroxide anion exchangers into cation exchangers by topotactic reactions using alkali metal sulfate solutions

Layered double hydroxides [Mn2Al(OH)6](An−)x/n·yH2O (An− = Cl− or NO3−) were exchanged with Na2SO4 and cationic/anionic exchangers [Mn6Al3(OH)18](SO4,NaSO4) were obtained.

Dinuclear neodymium and lanthanum bis(2,6-diisopropylphenyl) phosphate complexes bearing a hydroxide ligand: catalytic activity of the Nd complex in 1,3-diene polymerization

The reactions of K[(2,6-iPr2C6H3-O)2POO] either with LaCl3(H2O)7 or with Nd(NO3)3(H2O)6 in a 3:1 molar ratio, followed by vacuum drying and recrystallization from alkanes, have led to the formation of diaquapentakis[bis(2,6-diisopropylphenyl) phosphato]-μ-hydroxido-dilanthanum hexane disolvate, [La2(C24H34O4P)5(OH)(H2O)2]·2C6H14, (1)·2(hexane), and tetraaquatetrakis[bis(2,6-diisopropylphenyl) phosphato]-μ-hydroxido-dineodymium bis(2,6-diisopropylphenyl) phosphate heptane disolvate, [Nd2(C24H34O4P)4(OH)(H2O)4]·2C6H14, (2)·2(heptane). The compounds crystalize in the P21/n and P\overline{1} space groups, respectively. The diaryl-substituted organophosphate ligand exhibits three different coordination modes, viz. κ2 O,O′-terminal [in (1) and (2)], κO-terminal [in (1)] and μ2-κ1 O:κ1 O′-bridging [in (1) and (2)]. Binuclear structures (1) and (2) are similar and have the same unique Ln2(μ-OH)(μ-OPO)2 core. The structure of (2) consists of an [Nd2{(2,6-iPr2C6H3-O)2POO}4(OH)(H2O)4]+ cation and a [(2,6-iPr2C6H3-O)2POO]− anion, which are bound via four intermolecular O—H...O hydrogen bonds. The molecular structure of (1) displays two O—H...O hydrogen bonds between OH/H2O ligands and a κ1 O-terminal organophosphate ligand, which resembles, to some extent, the `free' [(2,6-iPr2C6H3-O)2POO]− anion in (2). NMR studies have shown that the formation of (1) undoubtedly occurs due to intramolecular hydrolysis during vacuum drying of the aqueous La tris(phosphate) complex. Catalytic experiments have demonstrated that the presence of the coordinated hydroxide anion and water molecules in precatalyst (2) substantially lowered the catalytic activity of the system prepared from (2) in butadiene and isoprene polymerization compared to the catalytic system based on the neodymium tris[bis(2,6-diisopropylphenyl) phosphate] complex, which contains neither OH nor H2O ligands.