Tris[(alkylthio)methyl]silanes:  Syntheses and Structures of Chromium, Molybdenum, and Tungsten Complexes with a Tripodal Thioether Ligand

Abstract

The first member of a new family of tripodal thioether ligands, the methyltris[(alkylthio)methyl]silanes MeSi(CH(2)SR)(3) (R = Me), has been synthesized and characterized. Reactivity studies lead to the isolation of the complete series of group 6 metal carbonyl derivatives {eta(3)-MeSi(CH(2)SMe)(3)}M(CO)(3) (M = Cr, Mo, W), whose structures have been determined by single-crystal X-ray diffraction. The three complexes are isomorphous and display distorted octahedral structures with face-capping tridentate thioether ligands. {eta(3)-MeSi(CH(2)SMe)(3)}Cr(CO)(3) is monoclinic, P2(1)/c, a = 8.1658(2) Å, b = 15.0563(2) Å, c = 26.5791(3) Å, beta = 90.3653(6) degrees, V = 3267.74(8) Å(3), Z = 8. {eta(3)-MeSi(CH(2)SMe)(3)}Mo(CO)(3) is monoclinic, P2(1)/c, a = 8.34630(6) Å, b = 15.2747(2) Å, c = 27.1865(4) Å, beta = 90.8987(9) degrees, V = 3465.44(10) Å(3), Z = 8. {eta(3)-MeSi(CH(2)SMe)(3)}W(CO)(3) is monoclinic, P2(1)/c, a = 8.1582(2) Å, b = 14.9903(2) Å, c = 26.7268(4) Å, beta = 90.6568(8) degrees, V = 3268.30(9) Å(3), Z = 8.

Kinetic and Thermodynamic Assessments of the Mediator−Template Assembly of Nanoparticles

“…The synthesis of methyltris[(methylthio)methyl]silane (MeSi(CH 2 SCH 3 ) 3 , TE 3 ) has been described previously. 28 Synthesis. Gold nanoparticles capped with monolayer shells of tetraoctylammonium bromide were synthesized using the twophase protocol.…”

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

“…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].…”

Formation of extended 1D coordination polymers in tetrathioether complexes of mercury(II): Effect of the organic substituents on the crystal structures of {Si(CH2SR)4}HgBr2 (R=Me, Ph)

“…The extended structures result from intermolecular Hg-S interactions linking the monomeric {Si(CH 2 SR) 4 }HgBr 2 units, as established for 2a, b using single-crystal X-ray diffraction. The effective coordination around the Hg atoms in both compounds is best described as distorted octahedral.We have recently reported the synthesis of the bidentate and tridentate thioethers R 4 À n Si(CH 2 SR) n (n = 2, 3; R = Me, Ph) and characterized a wide variety of complexes in which they act as either terminal [1][2][3][4][5] or bridging ligands [6,7]. The latter are particularly interesting since flexible multidentate ligands have the ability to generate diverse coordination networks with potential applications as functional materials [8-10] but the use of polythioethers in such context has received little attention [11][12][13][14][15][16].…”

“…65% yield. 1 The complexes [{Si(CH 2 SR) 4 }HgBr 2 ] (R = Me, 2a; R = Ph, 2b) were readily prepared by allowing mercury(II) bromide to react with equimolar amounts of the corresponding thioethers (Scheme 2) and were isolated as white, air-stable solids in 55-80% yield. They are both soluble in chlorinated hydrocarbons and were characterized by a combination of analytical and spectroscopic techniques.…”

“…The tetrathioether Si(CH 2 SMe) 4 (1a) was easily synthesized, following a procedure similar to that used to prepare MeSi(CH 2 SMe) 3 [1], by reacting tetrachlorosilane with 4 molar equivalents of LiCH 2 SMe (Scheme 1). Following vacuum distillation (b.p.…”