Fe(CO)5 promoted C–S bond activation and formation of an unusual C2S3 ligand in [{Fe2(CO)6}2(μ-C2S3)]

Transition-metal mediated carbon–sulfur bond activation and transformations

“…In this section, only a concise overview of C-S bond cleavage by stoichiometric amounts of transition metal compounds is presented although a variety of reports have been documented in this area. [1][2][3][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] Coordination models of thiophene rings to transition metals have been reported, demonstrating diverse C-S bond activation in the complexes (Scheme 1). 31 In particular, the insertion reactions of metal atoms to C-S bonds in thiophenes and other organosulfur compounds have been extensively studied in order to get better understanding of the heterogeneous HDS mechanisms.…”

“…[47][48][49] In the presence of an excessive amount of hydrosilane and with the help of an iron complex, i.e., [Cp(CO) 2 FeMe] (42), desulfurization of N,N-dimethylthioformamide was achieved (eqn ( 17)). 50 In the reaction sequence, silyl migration from Fe to S of thioformamide triggered the cleavage of a CQS bond to generate a carbene-iron complex which was isolated and characterized by X-ray crystallographic determination (eqn (18)). Reaction of the iron(II) complex (45) bearing the bulky N,N 0dimesityl-2,2 0 -diamidophenyl sulfide ligand with 3 equivalents of isocyanide afforded the low-spin complex [( mes NSN)Fe(CNR) 3 ] (R = Ph-2,6-Me 2 ) (46).…”

“…Photolysis of a hexane solution containing Fe(CO) 5 and CS 2 led to desulfurization and formation of a novel cluster [{Fe 2 (CO) 6 } 2 (m-C 2 S 3 )] (48) (eqn (19)). 18 Activation of the CQS bond is selective for the reaction of CS 2 with Fe(CO) 5 , and the unique C 2 S 3 ligand acts as a bridge between the two Fe 2 (CO) 6 units and forms an unusual ferrathiacyclobutene ring. Azoketene dithioacetals (49) were treated with Fe 2 (CO) 9 in anhydrous ethyl ether at room temperature to produce complex 50 as the major product by cleaving one of the C-S bonds in 49 (eqn (20)).…”

μ4-Orthothiocarbonato-tetrakis[tricarbonyliron(I)](2Fe—Fe)

“…For general background to related complexes, see: Mathur et al (2009). For uses of R 3 P/CS 2 in coordination chemistry and organometallic chemistry, see: Galindo et al (1999).…”

“…The cleavage of the C-S bonds is often observed in various transition metal complexes in which chemistry has been explored for the hydrosulfurization of fossil products. In these complexes, the S 2ion derived from the C-S bond scission functions as a bridging ligand to link metal ions and metal cluster fragments and is generally of use in various cluster growth processes (Mathur et al, 2009).…”