Coordination Chemistry of Silanedithiolato Ligands Derived from Cyclotrisilathiane:  Synthesis and Structures of Complexes of Iron(II), Cobalt(II), Palladium(II), Copper(I), and Silver(I)

Abstract

The coordination chemistry of chelating silanedithiolato ligands has been investigated on Fe(II), Co(II), Pd(II), Cu(I), and Ag(I). Treatment of M(OAc)(2) (M = Fe, Co, Pd) with cyclotrisilathiane (SSiMe(2))(3) in the presence of Lewis bases resulted in formation of Fe(S(2)SiMe(2))(PMDETA) (1), Fe(S(2)SiMe(2))(Me(3)TACN) (2), Co(S(2)SiMe(2))(PMDETA) (3), and Pd(S(2)SiMe(2))(PEt(3))(2) (4) (PMDETA = N,N,N',N',N' '-pentamethyldiethylenetriamine; Me(3)TACN = 1,4,7-trimethyl-1,4,7-triazacyclononane). The analogous reactions of M(OAc) (M = Cu, Ag) in the presence of PEt(3) gave rise to the dinuclear complexes M(2)[(SSiMe(2))(2)S](PEt(3))(3) [M = Cu (5), Ag (6)]. Complexes were characterized in solution by (1)H, (31)P[(1)H], and (29)Si[(1)H] NMR and in the solid state by single-crystal X-ray diffraction. Mononuclear complexes 1-3 have a four-membered MS(2)Si ring, and these five-coordinate complexes adopt trigonal-bipyramidal (for the PMDETA adducts) or square-pyramidal (for the Me(3)TACN adduct) geometries. In dimer 6, the (SSiMe(2))(2)S(2)(-) silanedithiolato ligand bridges two metal centers, one of which is three-coordinate and the other four-coordinate. The chelating effect of silanedithiolato ligands leads to an increase in the stability of silylated thiolato complexes.

Triaquabis(tri-tert-butoxysilanethiolato)barium

“…The structure and chemistry of silanethiolates have been a subject of research for about 20 years (Wojnowski et al, 1985;Becker et al, 1990;Preuss et al, 1990;Peters et al, 1997;Kovacs et al, 2000;Komuro et al, 2003). Most of the papers describe silanethiolates of transition metals (e.g.…”

The influence of alkane spacer of bis(diphenylphosphino)alkanes on the nuclearity of silver(I): Syntheses and structures of P,P′-bridged clusters and coordination polymers involving dithiophosphates

“…The study of silver-silver short contact in complexes, less than twice of van der Waal's radii of silver atom (3.40 Å), has invited attention of several research groups in the recent years [2][3][4][5][6][7][8], as such interaction has led to generate interesting electrical conducting properties [9,10]. The sulfur donor ligands have played an important role in the formation of such interactions due to their ability to bring two or more metals in close contact in view of angular flexibility at sulfur donor atoms [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16].…”

“…The sulfur donor ligands have played an important role in the formation of such interactions due to their ability to bring two or more metals in close contact in view of angular flexibility at sulfur donor atoms [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16]. Furthermore, silver-sulfur interactions are more covalent in nature due to the soft-soft acid-base interactions, and such interactions enhance the argentophilic character of silver atoms.…”

“…Some of the complexes disclose short silver-silver contacts. Structural characterization reveal the formation of tetranuclear, [ [Ag 4 (dppm) 2 4 (l 3 -Cl)(dppe) 1.5 {S 2 P(OR) 2 } 3 ] 1 (R = Et, 6a; i Pr, 6b)] polymers are obtained in the presence of dppe and dppb with longer spacer in the diphosphine backbone. A part of this work has been communicated earlier containing the description of 5a, 5b, 6a and 6b [1].…”

Dimeric and trimeric diorganosilicon chalcogenides (PhRSiE)2,3 (E=S, Se, Te; R=Ph, Me)

“…Recently Kawaguchi and coworkers [4,5] have demonstrated the potential of (Me 2 SiS) 3 as starting material in the preparation of several types of sulfide clusters of transition metals with S-SiMe 2 -S and S-SiMe 2 -SSiMe 2 -S ligands.…”