199859-00-2Relevant academic research and scientific papers
Hydrogenation of (1-phenylthiophene)Mn(CO)3 (thiophene = 3-methylthiophene and 3,4-dimethylthiophene) complexes: Formation of tetrakis(tricarbonyl-phenylthiomanganese)
Choi, Dai Seung,Hong, Soon Hyeok,Lee, Su Seong,Chung, Young Keun
, p. 385 - 390 (2007/10/03)
For the hydrogenation of (1-phenylthiophene)Mn(CO)3 (2), the nature of the thiophene derivatives strongly affect the yields and distribution of reaction products. When 3-methyl- and 3,4-dimethylthiophene were used as thiophene derivatives, the dimer [Mn(CO)4(SPh)]2 (7) and the tetramer [Mn(CO)3(SPh)]4 (8) was obtained as major products and the hydrodesulfurized product, isoprene or 2,3-dimethyl-1,3-butadiene were obtained in a high yield. Structures of 7 and 8 were verified by X-ray diffraction studies.
Models for the homogeneous hydrodesulfurization of thiophenes: Manganese-mediated carbon-sulfur bond cleavage and hydrogenation reactions
Dullaghan, Conor A.,Carpenter, Gene B.,Sweigart, Dwight A.,Choi, Dai Seung,Lee, Su Seong,Chung, Young K.
, p. 5688 - 5695 (2008/10/08)
Chemical reduction of a series of (η5-thiophene)Mn(CO)3+ complexes (3a-d) under an atmosphere of CO affords dimanganese metallathiacyclic complexes (4a-d), which have a Mn(CO)4 moiety regioselectively inserted into a C-S bond. Reaction of 4 with H2, the rate of which is strongly influenced by substituents on the thiophene ring, leads to hydrogenolysis of the Mn-C σ-bond and formation of (OC)3Mn(μ-H)(μ-SCRCHCHCHR′)Mn(CO)3 (8; R, R′ = H, Me), which contains bridging hydride and thiolate ligands and a Mn-Mn bond. The addition of PhMgBr to 3 occurs at the sulfur to give zwitterionic complexes (6a-c, 14), which undergo regioselective hydrogenolysis of a C-S bond and, in some cases, partial desulfurization with concomitant formation of (OC)4Mn(μ-H)(μ-SPh)Mn(CO)4 (5a). Crystal structures are reported for complexes 4b,d, 5a, 8d, 10, 12c, and 14b,c. It is suggested that the reactions reported herein may be relevant to the general problem of hydrodesulfurization (HDS) of thiophenic molecules.
