Selective Removal of Sulfate from Water by Precipitation with a Rigid Bis-amidinium Compound.

A simple, readily prepared biphenyl bis-amidinium compound (1⋅Cl2 ) is able to selectively precipitate sulfate from water. The precipitant is effective at concentrations as low as 1 mM and shows complete selectivity against monovalent anions, and high selectivity even against CO3 2- and HPO4 2- . It is highly effective (>90 % sulfate removed) in both seawater and highly acidic conditions relevant to mining waste-streams. X-ray crystallography reveals that 1⋅SO4 forms a tightly packed, anhydrous, structure where each sulfate anion receives eight hydrogen bonds from amidinium N-H hydrogen bond donors.

Room Temperature Hydrolysis of Benzamidines and Benzamidiniums in Weakly Basic Water.

Benzamidinium compounds have found widespread use in both medicinal and supramolecular chemistry. In this work, we show that benzamidiniums hydrolyze at room temperature in aqueous base to give the corresponding primary amide. This reaction has a half-life of 300 days for unsubstituted benzamidinium at pH 9, but is relatively rapid at higher pH's (e.g., t1/2 = 6 days at pH 11 and 15 h at pH 13). Quantum chemistry combined with first-principles kinetic modeling can reproduce these trends and explain them in terms of the dominant pathway being initiated by attack of HO- on benzamidine. Incorporation of the amidinium motif into a hydrogen bonded framework offers a substantial protective effect against hydrolysis.

What's in an Atom? A Comparison of Carbon and Silicon-Centred Amidinium⋠⋠⋠Carboxylate Frameworks*.

Despite their apparent similarity, framework materials based on tetraphenylmethane and tetraphenylsilane building blocks often have quite different structures and topologies. Herein, we describe a new silicon tetraamidinium compound and use it to prepare crystalline hydrogen bonded frameworks with carboxylate anions in water. The silicon-containing frameworks are compared with those prepared from the analogous carbon tetraamidinium: when biphenyldicarboxylate or tetrakis(4-carboxyphenyl)methane anions were used similar channel-containing networks are observed for both the silicon and carbon tetraamidinium. When terephthalate or bicarbonate anions were used, different products form. Insights into possible reasons for the different products are provided by a survey of the Cambridge Structural Database and quantum chemical calculations, both of which indicate that, contrary to expectations, tetraphenylsilane derivatives have less geometrical flexibility than tetraphenylmethane derivatives, that is, they are less able to distort away from ideal tetrahedral bond angles.

A three dimensional hydrogen bonded organic framework assembled through antielectrostatic hydrogen bonds.

A crystalline 3D hydrogen bonded framework is assembled in water from tetrahedral tetraamidinium cations and antielectrostatically hydrogen bonded bicarbonate dimers. The framework forms in water, and represents a clear demonstration of the potency of these anti-Coulombic hydrogen bonds. Gentle heating of the framework (50 °C) releases CO2 and water to give the neutral tetraamidine compound.