117526-77-9Relevant academic research and scientific papers
Synthesis and structural characterization of sulfur rich iron (II) carbonyl dimers: Facile reversible reaction with carbon monoxide
Carcer, Inigo Aguirre de,Heinekey, D. Michael
, p. 840 - 844 (2009)
The sulfur-rich iron carbonyl dimer complexes [Fe(CO)2(S′SiS2)]2 (2), and [Fe(CO)(S′SiS2)]2 (3) have been prepared. The [2Fe-2S] cores of the new complexes are planar. The binding mode of the tridentate sulfur ligand in complex 2 is facial with a S(thiolate)-Fe-S(thiolate) angle of 92°, while in complex 3, the S′SiS2 ligand binds the metal with a S(thiolate)-M-S(thiolate) angle of 120°. The Fe-Fe distance is reduced from 3.45 A? in complex 2 to 2.78 A? in the 32 electron dimer complex 3. Complexes 2 and 3 are at equilibrium in solution and can be readily interconverted by addition or removal of CO.
Synthesis of Dibenzo[d,g][1,3,6]trithiocins
Maruta, Teruo,Sugihara, Yoshiaki,Tanaka, Sanae,Ishii, Akihiko,Nakayama, Juzo
, p. 1187 - 1192 (1998)
6-Acetoxy-, 6-methoxy-, 6-azido-, and 6-(methylthio)dibenzo[d,g][ 1,3,6]trithiodns (13,14,17, and 18, respectively) were synthesized by reactions of 9aH-9,10-dithiu-4b-thioniaindeno[ 1,2-a]indene chloride (4) with appropriate micleophiles in good yields.
Transition Metal Complexes with Sulfur Ligands, 138 Synthesis, Structures, and Reactions of Sulfur-Rich Nickel and Platinum Complexes with [MS3] and [MNS2] Cores
Sellmann, Dieter,Haeussinger, Daniel,Heinemann, Frank W.
, p. 1715 - 1726 (2007/10/03)
Nickel and platinum complexes with tridentate ligands, having [S3] or [NS2] donor sets were investigated in order to model active sites of enzymes such as hydrogenases or CO dehydrogenases. Starting from diphenyl sulfide, a preparative synthesis was developed for 'S3'-H2 ['S3'-H2=bis(2-mercaptophenyl) sulfide]. Reactions of 'S3'-H2 or anionic 'S3'(2-) with nickel and platinum precursors resulted in the formation of binuclear [Ni('S3')]2 (1) and trinuclear [Pt('S3')]3 (5). Complex 1 was cleaved by PMe3 or CN(1-) to give the mononuclear complexes [Ni('S3')(PMe3)] (2) and NMe4[Ni('S3')(CN)] (3). Attempts to coordinate hydride to the [Ni('S3')] fragment led to C-S bond cleavage of the ligand and formation of (NMe4)2[{Ni(μ-SC6H5)(S2C6H4)}2] (4). Oxidative addition of Li['S3'-H] to [Pt(PPh3)4] afforded the platinum hydride complexes Li[Pt(H)('S3')] and Li[Pt(H)(PPh3)('S3')] which, however, could not be separated from each other and yielded [Pt('S3')(PPh3)] (6) when treated with MeOH. In order to investigate electronic effects of the donor set, the 'S3' ligand was modified by alkylation of one thiol group to give 'RS3'-H derivatives (R=Me, Et, Cy) and by replacing a mercaptophenyl unit by an amine in 'Et2NS2'-H ['Et2NS2'-H=N,N-diethyl-2-(2-mercaptothiophenyl)ethylamine]. Reactions of Ni(II) or Ni(0) compounds with these ligands in a 1:1 ratio yielded the 1:2 complexes [Ni('MeS3')2] (7), [Ni('EtS3')2] (9) and [Ni('CyS3')2] (10), with 'RS3'(1-) acting as bidentate ligands only. Complex 7 reversibly reacted with PMe3 to form cis-[Ni(PMe3)2('MeS3')2] (8), exhibiting monodentate 'MeS3' ligands. [Ni('Et2HNS2')2]Br2 (11) reeacted reversibly with bases to presumably give octahedral [Ni('Et2NS2')2]. Complexes 7, 9 and 10 also did not yield any [Ni('RS3')(H)] hydride complex when treated with hydride sources. Oxidative addition of 'CyS3'-H to [Pt(PPh3)4] yielded the hydride complexes [Pt(H)('CyS3')] and [Pt(H)(PPh3)('CyS3')] which, however, formed an inseparable mixture and underwent C-S bond cleavage when heated, affording [Pt(o-S2C6H4)(PPh3)2]. The molecular structures of 1, 2, 3, 5, 6, 7, and 11 were determined by X-ray crystallography, revealing butterfly-like shapes for the [MS3L] cores of the complexes.
