Linkage Scrambling in Branched Chain Polymercury Compounds: Nitrides from the Mercury‐Mediated Disproportionation of N₂O₃

Abstract

A novel nitride‐polymercury nitrate, Hg4N(NO3)3, 1, crystallizes spontaneously from the room temperature reaction of mercury metal and solvent‐stabilized N2O3. In addition to an unusual synthesis, composition, and structure, this compound is rare among metal nitrates for its lack of reactivity with water. Analysis by IR, single and powder X‐ray crystallography, XPS, NMR, DSC, and cyclic voltammetry demonstrates its unique composition and places it at the nitrogen‐rich end of the range of [X(Hg4)](NO3)3, X = O, OH, or N, polymercurys.

Preparation of Dinitrogen Trioxide for Organic Synthesis: A Phase Equilibrium Approach

“…As N 2 O 3 can be stabilized by solvation (Scheme 2), its solutions (up to 1 M N 2 O 3 ) can be stable at 0 °C under p(NO) � 1700 mbar and used for reactions at room temperature. [11,79,80] Comparing with the preparation of pure N 2 O 3 (Section 3.1), the requirement on condition control is attenuated, making N 2 O 3 solution relatively accessible for synthetic chemists.…”

“…Because of the limited specific g/l interface for the mass transport, the operation is slow and cumbersome. Even though, this method is still handy to prepare a few milliliter of N 2 O 3 solution for qualitative experiments [79,80] …”

“…Even though, this method is still handy to prepare a few milliliter of N 2 O 3 solution for qualitative experiments. [79,80] In continuous flow reactors (Scheme 7c), where there is no head space, the gases can be completely dissolved (V g = 0, P = 1) when the ratio of flow rates of NO and O 2 lies between 2 (NO 2.0 ) and 4 (NO 1.5 ). When the ratio of flow rates NO/O 2 = 4, the concentration of N 2 O 3 (c l ) in the homogeneous liquid flow is an independent variable that can be precisely controlled by setting the flow rates of the solvent (V l ) and the gases (n) on pumps and mass flow controllers (MFC) respectively.…”

“…These solvents are generally anhydrous non‐reductive aprotic solvents; N 2 O 3 is more prone to dissociate in apolar solvents than in polar aprotic solvents [9] (e. g. CCl 4 and MeCN in Scheme 2). As N 2 O 3 can be stabilized by solvation (Scheme 2), its solutions (up to 1 M N 2 O 3 ) can be stable at 0 °C under p (NO)≈1700 mbar and used for reactions at room temperature [11,79,80] . Comparing with the preparation of pure N 2 O 3 (Section 3.1), the requirement on condition control is attenuated, making N 2 O 3 solution relatively accessible for synthetic chemists.…”