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Mercury(II) and Methylmercury(II) Complexes of Novel Sterically Hindered Thiolates: 13C and 199Hg NMR Studies and the Crystal and Molecular Structures of [MeHg(SC6H2-2,4,6-Pr'3) ], [Hg(SC6H4-2-SiMe3)2], [Hg(2-SC5H3N-3-SiMe3)2], and [Hg|<2-SC6H4)2SiMe2|]2

larger effective radius of the N(CH,),C ion compared with the alkali-metal ions, presumably rule out any significant intermolecular interactions. h g . I . Perspective drawing of the crystal structure of N(CH&O, (H atoms omitted).The alkali-metal ozonides undergo exothermic decomposition according to the following equation:Oxygen transport in the solid probably involves initial transfer of the oxygen atoms of the 0; ions to hyperoxide ions formed on the surfaces. It is easy to imagine how the larger intermolecular 0-0 distances in the case of N(CH3)403 make this reaction more difficult and thus may explain its unexpected high thermal stability. This interpretation is supported by the fact that N(CH3),03 decomposes by a mechanism different from that for the alkalimetal ozonides. MS and DTA/TG investigations indicate that the first step is an oxidative attack on the cation, resulting in exothermic formation of the white crystalline substance mentioned above, which, above ca. I O O T , decomposes into gaseous products, identified by mass spectrometry as N(CH3)3, CO, 02, H 2 0 , (CH&O, CH30H, and C3H,N0 (possibly DMF).The synthesis and structural elucidation of N(CH3),03 demonstrate, for the first time, the stability of the 0; ion in the presence of cations other than alkali-metal ions. The surprisingly high stability, which is mainly determined by the intermolecular 0-0 distances, points the way toward the synthesis of even more stable ozonides.