One-Dimensional Copper(I) Coordination Polymers Based on a Tridentate Thioether Ligand

Abstract

The one-dimensional copper(I) coordination polymers Cu(3){MeSi(CH(2)SMe)(3)}(2)X(3) (X = Cl, Br) and [{MeSi(CH(2)SMe)(3)}Cu(NCMe)]Y (Y = OSO(2)CF(3), BF(4), PF(6)) were readily obtained in very good to excellent yields (80-95%) by reacting CuX or [Cu(NCMe)(4)]Y, respectively, with the tridentate thioether ligand MeSi(CH(2)SMe)(3) in acetonitrile. The new complexes were characterized by a combination of analytical and spectroscopic techniques, including electrospray ionization mass spectrometry and, for the bromo and hexafluorophosphate derivatives, single-crystal X-ray diffraction. Both complexes exhibit one-dimensional chain structures with approximately tetrahedral copper centers and bridging unidentate/bidentate thioether ligands.

Di-μ-iodo-bis{[methyltris(methylthiomethyl)silane-κ2S,S′]copper(I)}

“…Prompted by our interest in a systematic investigation of tripodal thioethers of general formula MeSi(CH 2 SR) 3 , we recently reported the preparation of MeSi(CH 2 SMe) 3 and the synthesis and structural characterization of its group 6 metal tricarbonyl derivatives {MeSi(CH 2 SMe) 3 }M(CO) 3 (M = Cr, Mo, W) (Yim, Tran, Dobbin et al, 1999). In contrast to the mononuclear nature of these complexes, the reactions of MeSi(CH 2 SMe) 3 with the copper(I) halides CuX (X = Cl, Br) yielded one-dimensional coordination polymers of stoichiometry Cu 3 {MeSi(CH 2 SMe) 3 }X 3 (Yim, Tran, Pullen et al, 1999). Unexpectedly, the corresponding reaction of CuI, under similar conditions, produced a 1:1:1 species of composition {MeSi(CH 2 SMe) 3 }CuI, which we initially assumed to be analogous to the mononuclear crown thioether derivative (9S3)CuI (Ku È ppers et al, 1987).…”

Bis(thioether)silanes: Synthesis and characterization of tin(IV) complexes with new dithioether ligands

“…The tris(thioether)silanes MeSi(CH 2 SR) 3 (abbreviated Tts R , where R ¼ alkyl or aryl) constitute a versatile family of chelating thioether ligands that are easily prepared in good yields (60 -80%), are thermally robust and air-stable, and readily dissolve in a variety of organic solvents, including alcohols. Although their coordination chemistry is yet to be fully exploited, a number of transition and main group metal complexes thereof have been synthesized in recent years, including group 6 metal tricarbonyl derivatives (Tts R )M(CO) 3 (M ¼ Cr, Mo, W) [1,2] and polynuclear compounds of copper(I) [3,4] and bismuth(III) [5].…”

“…Although their coordination chemistry is yet to be fully exploited, a number of transition and main group metal complexes thereof have been synthesized in recent years, including group 6 metal tricarbonyl derivatives (Tts R )M(CO) 3 (M ¼ Cr, Mo, W) [1,2] and polynuclear compounds of copper(I) [3,4] and bismuth(III) [5]. The syntheses of the tetradentate thioethers Si(CH 2 SR) 4 (R ¼ Me, Ph) and their mercury(II) derivatives {Si(CH 2 SR) 4 }HgBr 2 , both of which exhibit one-dimensional polymeric structures in the solid state, have also been reported [6].…”

Thiol−Ene Reaction for the Synthesis of Multifunctional Branched Organosilanes

“…The reactions proceed in high yield under photochemical irradiation. In addition to serving as cores for divergent dendrimer growth, these compounds may also be viewed as potential multipodal chelators [20][21][22][23][24][25][26][27][28][29] or stabilizers of transition-metal nanoparticles. [30][31][32][33]…”