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ABSTRACT: A new tridentate thioether ligand, methyltris[(methylthio)methyl]silane MeSi(CH2SMe)3, has been synthesized with the goal of investigating the coordination chemistry of acyclic polythioethers. This ligand represents the first member of a new family of face-capping, tridentate thioether ligands which are related to the well known macrocyclic thioether 1,4,7-trithiacyclononane and also to the anionic tetrakis[(methylthio)methyl]borates. Initial reactivity studies of the newly synthesized thioether ligand resulted in the successful isolation and structural characterization of the complete series of group 6 carbonyl derivatives ([eta symbol3]-MeSi(CH2SMe)3)M(CO)3(M = Cr, Mo, W). The copper(I) coordination polymers Cu3(MeSi(CH2SMe)3)2X3(X = Cl, Br) and [(MeSi(CH2SMe)3)Cu(NCMe)]Y (Y = OSO2CF3, BF4, PF6) were isolated by reacting CuX or [Cu(NCMe)4]Y, respectively, with the ligand. The reaction of the ligand in a 1:1 molar ratio with CuI yielded (MeSi(CH2SMe)3)CuI, which has been structurally characterized and found to form a dimer in the solid state. Related silver(I) derivatives based on the thioether ligand were also synthesized and characterized. The investigation of the behavior of these complexes in acetonitrile solution was conducted using electrospray ionization mass spectrometry (ESI-MS). Reactions of the ligand with BiX3(X = Cl, Br) afforded complexes of stoichiometry Bi2(MeSi(CH2SMe)3)2X6 and the chloride derivative was also found to be polymeric.
ABSTRACT: The new thioethers MeSi and Si have been synthesized with the goal of investigating the effect of the tert-butyl substituents on their structure and coordination chemistry. These tridentate or tetradentate ligands are new members of existing families of acyclic thioethers. Reactivity studies of these newly synthesized ligands were performed by coordinating them to group 6 metal carbonyl derivatives. These complexes have been compared with the group 6 metal complexes of other thioether ligands to determine the electronic and steric differences that the tert-butyl group may cause. Spectroscopic and X-ray diffraction studies were performed to determine those effects.
ABSTRACT: The new acyclic tetradentate thioether ligand tetrakis[(methylthio)methyl]silane, has been synthesized with the goal of studying its coordination chemistry and comparing it with that of the recently prepared methyltris[(methylthio)methyl]silane, and other tridentate or tetradentate thioethers. This new tetradentate ligand was coordinated to the group 6 transition metals to give a complete series of thioether carbonyl complexes, where the sulfur ligand is bound to the metal center in either a bidentate or tridentate fashion. The dinuclear compounds were obtained from the reaction of LM(CO)4 and [Cu(NCMe)4]X (X = BF4 or PF6) in a 2:1 ratio, with the thioether serving as a bridging ligand between the two metals. Furthermore, six and seven-coordinated dihalo thioether complexes have also been prepared and structurally characterized.
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