Step-by-step replacement of cyano groups by tricyanovinyls – the influence on the acidity

The dataset includes supporting information files for the article "Step-by-step replacement of cyano groups by tricyanovinyls – the influence on the acidity". The dataset contains results of optimization and frequency calculations carried out by Turbomole and Gaussian. Acid-base properties are the simplest expression of compounds’ coordinating ability. In the present work, we studied in silico how the gas-phase Brønsted acidity (GA) of several polycyano substituted compounds change when cyano (CN) groups are replaced by 1,2,2-tricyanovinyl (TCNV) groups in cyanic acid, dicyanoamine, cyanoform, and hydrogen tetracyanoborate. Different tautomers and conformers/isomers are included in the study. Gas-phase acidity values are compared with the acidities of different acids, including percyanated protonated mono-carba-closo-dodecaborate (carborane acid) and dodecaborate, as well as hydrogen cyanide and 1,2,2-tricyanoethene. An estimation of acetonitrile, dimethylsufoxide, and 1,2-dichloroethane acidities are presented using the COSMO-RS method and correlational analysis. The strongest acid with four TCNV groups shows remarkable acidic properties

Theoretical Study on Fluorinated Derivatives of Sulfolane, Cyclopentanone, and Gamma-Butyrolactone

In this paper, fluorinated compounds based on sulfolane, cyclopentanone, and gamma-butyrolactone are studied computationally, focusing on their applicability in electrochemical devices and acid–base-related studies. Candidates for solvents with (1) high polarity, (2) good electrochemical stability, and (3) low basicity were searched for. Some of the compounds are studied here for the first time. Electrochemical stabilities, dielectric constants, boiling points, basicities, and lipophilicities were estimated using DFT and COSMO-RS methods with empirical corrections. The effect of fluorination on these properties as well as the bond parameters was studied. The possible synthesis routes of the proposed compounds are outlined. Some molecules display a combination of estimated properties favorable for a solvent, although none of the studied compounds are expected to surpass acetonitrile and propylene carbonate by the width of the electrochemical stability window

pKaH values and θH angles of phosphanes to predict their electronic and steric parameters

Phosphanes have numerous important uses and at the same time are an important class of organic bases with basicities spanning more than 30 orders of magnitude. In many cases, their behaviour in specific applications depends strongly on their basicity. Basicities (pKaH values) of many phosphanes have been published but are scattered across different reports and there are prominent gaps in the availability of data. In this report, we present an extensive set of pKaH data of a most diverse set of phosphanes, both newly measured/calculated and collected from the literature. We demonstrate that pKaH values can serve as an alternative to Tolman electronic parameters (TEP values) in evaluating the electronic properties of phosphanes. Additionally, we suggest two easily obtainable parameters for assessing the steric properties of phosphaneswithout need for sophisticated calculations or preparation of metal-ligand complexes

A comprehensive self-consistent spectrophotometric acidity scale of neutral Brønsted acids in acetonitrile. J Org Chem. 2006; 71:2829–2838. [PubMed: 16555839

Abstract For the first time the self-consistent spectrophotometric acidity scale of neutral Brønsted acids in acetonitrile (AN) spanning 24 orders of magnitude of acidities is reported. The scale ranges from pK a value 3.7 to 28.1 in AN. The scale includes altogether 93 acids that are interconnected by 203 relative acidity measurements (∆pK a measurements). The scale contains compounds with gradually changing acidities, including representatives from all the conventional families of OH (alcohols, phenols, carboxylic acids, sulfonic acids), NH (anilines, diphenylamines, disulfonimides) and CH acids (fluorenes, diphenylacetonitriles, phenylmalononitriles). The CH acids were particularly useful in constructing the scale because they do not undergo homo-or heteroconjugation processes and their acidities are rather insensitive to traces of water in the medium. The scale has been fully cross-validated: the relative acidity of any two acids on the scale can be found combining at least two independent sets of ∆pK a measurements. The consistency standard deviation of the scale is 0.03 pK a units. Comparison of acidities in many different media 2 has been carried out and the structure-acidity relations are discussed. The large variety of the acids on the scale, its wide span and the quality of the data make the scale a useful tool for further acidity studies in acetonitrile.

Tris(benzophenoneimino)phosphane and related compounds

The dataset includes files supporting the article named "Tris(benzophenoneimino)phosphane and related compounds". Monocrystal XRD data, calculated .cosmo files, calculated pKaH values for related and correlation compounds, gas-phase geometry optimization and frequency calculation files, and NMR files are given

Janus face all-cis 1,2,4,5-tetrakis(trifluoromethyl)- and all-cis 1,2,3,4,5,6-hexakis(trifluoromethyl)- cyclohexanes

Authors thank the Engineering and Physical Sciences Research Council (EPSRC) for funding and the Chinese Scholarship Council for a studentship (CY).We report the synthesis of all‐cis 1,2,4,5‐tetrakis (trifluoromethyl)‐ and all‐cis 1,2,3,4,5,6‐hexakis (trifluoromethyl)‐ cyclohexanes by direct hydrogenation of precursor tetrakis‐ or hexakis‐ (trifluoromethyl)benzenes. The resultant cyclohexanes have a stereochemistry such that all the CF3 groups are on the same face of the cyclohexyl ring. All‐cis 1,2,3,4,5,6‐hexakis(trifluoromethyl)cyclohexane is the most sterically demanding of the all‐cis hexakis substituted cyclohexanes prepared to date, with a barrier (ΔG) to ring inversion calculated at 27 kcal mol−1. The X‐ray structure of all‐cis 1,2,3,4,5,6‐hexakis(trifluoromethyl)cyclohexane displays a flattened chair conformation and the electrostatic profile of this compound reveals a large diffuse negative density on the fluorine face and a focused positive density on the hydrogen face. The electropositive hydrogen face can co‐ordinate chloride (K≈103) and to a lesser extent fluoride and iodide ions. Dehydrofluorination promoted decomposition occurs with fluoride ion acting as a base.Publisher PDFPeer reviewe