Approach to Di/Triorganotin(IV) Cations via Hydrolysis of Stannate Salts Bearing Alkanesulfonate Ligands.

An in-depth study of the class of organotin cations bearing weakly coordinating trifluoromethanesulfonate/arylsulfonate has led to key insights into their stability, structural aspects, and role as catalysts. Related chemistry with alkanesulfonate ligands remains a missing link due to the strong Sn-O bond. The study reported herein describes the scope of diorganostannates, [-BuN][RSn(OSOR)] (R = -Bu, R = Me(), Et(); R = Ph, R = Me()), as reactive substrates in the presence of adventitious water to afford [-BuSnOH(OSOMe)] (), [-BuSn(HO)][-BuN][OSOEt]·HO (), and [PhSn(HO)][-BuN][OSOMe] (), respectively, the latter two being the first examples of salt cocrystals comprising tetra(aqua)diorganotin cations.

Insight into the High Proton Conductivity of One-/Two-Dimensional Cadmium Phosphites.

The study describes the synthesis and structural attributes of two new cadmium phosphites, [Cd{OP(O)(OH)H}(4,4'-bipy)] () and [Hpip][Cd(HPO)(HO)]·HO (). The structure of adopts a two-dimensional motif featuring alternate [Cd-μ-O] and [Cd-O-P-O]-cyclic rings, while the inorganic chains are held together by 4,4'-bipyridine. The presence of strong hydrogen bonding interactions between the appended HPO groups (O---O = 2.

Studies on the Genesis and Proton Conductivity of Imidazole-Based Linear and Open-Framework Zinc Phosphites.

Three new zinc phosphites, [HIm][Zn(HPO)] (), [Zn(HPO)Im] (), and [Zn(HPO)Im] () (Im = imidazole), have been synthesized from the hydro/solvothermal reaction of zinc acetate, dimethyl phosphite, and imidazole by varying the temperature and solvent of the reaction medium. The structure of is built from vertex-sharing of four HPO-capped ZnP units and adopts an open framework with 12-ring channels stabilized by HIm cations via N-H···O hydrogen bonds. For , the inorganic skeleton is comprised of alternating ZnO and HPO tetrahedra, while the coordinatively associated ZnNO fragments occupy the 12-ring hexagonal channels.

Tailoring Structural Diversity in Dimethyltin Carboxylates by the pH-Controlled Hydrothermal Approach.

The study presents a rational synthesis of new dimethyltin carboxylates, MeSn(Hbtec) (), MeSn(btec)(), [MeSn(HO)(btec)]·HO (), and [{MeSnOSn(OH)Me}(MeSnOH)(btec)]·HO (), derived from tetratopic 1,2,4,5-benzenetetracarboxylic acid (Hbtec). The method relies upon hydrothermal reaction (130 °C, 72 h) of dimethyltin dichloride and Hbtec under optimized pH (2 < pH < 8) conditions that allow control over dimethyltin speciation in aqueous medium as well as degree of deprotonation of the tetrafuntional carboxylic acid. The formation of a three-dimensional assembly in is assisted by the bridging bidentate (μ) mode of the carboxylate and O-H···O hydrogen bonds involving -COOH groups.