Cobalt(III)-Mediated Disulfuration and Hydrosulfuration of Alkynes

Abstract

Disulfuration and hydrosulfuration of alkynes mediated by an unusual square-planar tetrathiolate cobalt(III) complex [Cp 2Co] (+)[Co(S 2C 2B 10H 10) 2] (-), 1, lead to a series of cobalt-free carboranyl vinyl sulfides 2- 9. All new complexes 1, 2, 3, 4, 5, 6, 7, 8, and 9 were characterized by NMR spectroscopy ( (1)H, (11)B, (13)C), and X-ray structural analyses were performed for 1, 2, 3, 5, 6, 7, and 9.

Formation of multifunctional ligands by nucleophilic addition of alcohols and thiols to the alkyne groups in compound C5H5FeC5H4CCSCCH: Reactivity studies

“…In order to make an accurate assignment of the 13 (4), C 6 F 5 (6)] are obtained from analogous reactions by using a big excess of the HSR instead (Scheme 1). The 1 H and 13 C{ 1 H} NMR data are indicative of the presence in the molecule of two olephinic groups as a consequence of a double hydrothiolation (see Section 4) and they are in the range expected for comparable derivatives [17]. 1D-NOE experiments suggested a Z,Z stereochemistry at the two double carbon-carbon bonds.…”

“…According to the mechanisms described for these authors, we agree that once the complex [{Co 2 (CO) 6 } 2 (l-g 2 :g 2 -FcCCSCCH)] is formed, it can react with a molecule of the alkyne [{Co 2 (CO) 6 }(l-g 2 -FcCCSC"CH)] followed by another molecule of the ferrocenyl alkyne [{Co 2 (CO) 6 }(l-g 2 -FcC"CSCCH)] to give the trimerization product [{Co 2 (CO) 6 } 3 -(l-g 2 -FcCCS) 2 (l-g 2 -HCCS)]C 6 H 2 Fc after demetallation. Its spectroscopic and spectrometric data are the following: IR (m CO 2092m, 2061 s, 2030 vs), 1 H NMR {7.19 (s, 2H, C 6 H 2 ), 6.77 (s, 1H, HC"C), 4.54-4.36 (m, 12H, C 5 H 4 ), 4.34 (s, 5H, C 5 H 5 ), 4.31 (s, 5H, C 5 H 5 ), 4.20 (s, 5H, C 5 H 5 }, MS(ESI + ) m/z: 1488-1152 (M + ÀnCO, n = [6][7][8][9][10][11][12][13][14][15][16][17][18].…”

Ferrocene‐Substituted Dithio‐o‐Carborane Isomers: Influence on the Native Conformation of Myoglobin Protein

“…This could be explained by their solid‐state structures. FcSB1 has a tripod structure with two environmentally equivalent sulfur atoms,9a whereas FcSB2 contains a bent six‐membered ring with the S(2) atom showing less steric hindrance for coordination 9b. Moreover, the existence of the vinyl group between the ferrocenyl group and S(2) in FcSB2 should enhance electrochemical alterations.…”

Chloridobis(ethane-1,2-diamine)(4H-1,2,4-triazole-κN1)cobalt(III) dichloride

“…Appropriate tailoring of the coordination environment and specific incorporation of ligands around transition metal ions are of key importance in the modification of the properties of metal complexes with respect to spectroscopic, redox activity in interfacial electron-transfer reactions, catalytic and photocatalytic properties (Xu et al, 2008;Anbalagan, 2011). As a result of the excellent coordination ability of nitrogen-containing ligands, research on transition metal complexes involving ligands that coordinate through an N atom, such as simple amines (Mitzi, 1996;Deeth et al, 1984), cyanides (Wu et al, 2003;Shores et al, 2002), or N-heterocyclic rings (Hagrman et al, 1999;Willett et al, 2001), has always been an active area in coordination chemistry.…”