3‐ and 3,6‐Silylated 2‐Pyridinethiols: New Hindered Bidentate Ligands and Their Novel Silver and Copper Clusters

Abstract

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.

Synthesis and Structural Characterization of Copper(I), Silver(I) and Gold(I) Complexes with Pyrimidine‐2‐thionato Ligands and their Adducts with Phosphanes

“…The Cu–S [2.21287(16) and 2.2668(2) Å] and Ag–S [2.4514(14)–2.4996(13) Å] bond lengths are in agreement with those found for other Cu I [2.225(7)–2.2906(13) Å] [46–48,50] or Ag I [2.439(4)–2.529(4) Å]9a,47–50 hexanuclear complexes with heterocyclic thionato ligands in which the metal atoms are in a similar trigonal planar environment.…”

Hexakis(μ3-pyridine-2-thiolato-κ3N:S:S)hexasilver(I), [Ag6(μ3-SPy)6]

“…Each thiolate S atom bridges two Ag I atoms. The AgÐS distances are in the range 2.459 (3)±2.488 (3) A Ê and the AgÐN bond distances range from 2.307 (8) to 2.320 (8) A Ê ; these are very similar to those found in other hexanuclear complexes of silver with derivatives of pyridine-2thiolate (Nomiya et al, 2000;Block et al, 1988;Garcia-Vazquez et al, 2000).…”

Synthesis, spectral, thermal and structural characterization of a hexanuclear copper(I) cluster and a cobalt(III) complex of 1-ethyl-3-phenyl-thiourea

“…Recent work on copper(I) complexes has involved the synthesis and characterization of polynuclear complexes with bridging ligands [12]. Heterocyclic thiones, such as pyridine-2-thione [13] or 3-trimethylsilylpyridine-2-thione [14], form hexanuclear copper(I) complexes which have an interesting paddle-wheel like structure with an octahedral Cu 6 core. In these complexes each ligand, with the thione form [-NHC(@S)-], is converted to the thiolato form [-N-C(S-)-] and acts as an effectively tridentate ligand with a monodentate nitrogen atom and a bridging sulfur atom [15].…”