21240-14-2Relevant academic research and scientific papers
Carbon monoxide release properties and molecular structures of phenylthiolatomanganese(i) carbonyl complexes of the type [(OC)4Mn(μ-S-aryl)]2
Mede, Ralf,Lorett-Velsquez, Vaneza Paola,Klein, Moritz,G?rls, Helmar,Schmitt, Michael,Gessner, Guido,Heinemann, Stefan H.,Popp, Jürgen,Westerhausen, Matthias
, p. 3020 - 3033 (2015)
Several phenylthiolatomanganese carbonyl complexes of the type [(OC)4Mn(μ-SR)]2 (R = Ph (1a), C6H4-4-CH3 (1b), C6H4-4-CF3 (1c), C6H4-4-F (1d), C6H4-4-Cl (1e), C6H4-4-OMe (1f), C6F5 (1g), and CH2C6H4-4-Cl (1h)) have been prepared via the reaction of Mn2(CO)10 with diaryldisulfane or via the reaction of [(OC)5MnBr] with arylthiols. These complexes lose two carbon monoxide molecules quite easily yielding tetranuclear [(OC)3Mn(μ3-SR)]4 (2). Derivatives with fluoro-substituted aryl groups commonly form mixtures of dinuclear 1 and tetranuclear 2 which can quantitatively be converted to 2 by heating of the corresponding reaction mixtures. A unique trinuclear structure is found for the mesityl derivative [(OC)4Mn(μ-SMes)]3 (3) which is maintained in solution as verified by IR and NMR spectroscopy. Traces of an already known dinuclear by-product of the type [(OC)3Mn(μ-SC6H3(-4-Me)-2-SC6H4-4-Me)]2 (4) have been structurally characterized. The suitability of [(OC)4Mn(μ-SPh)]2 (1a) as a CO releasing molecule (CORM) for the administration of carbon monoxide has been studied. Two CO molecules are released upon dissolving in strongly Lewis basic solvents L, yielding [(OC)3Mn(L)(μ-SPh)]2, which liberates all the remaining CO molecules upon irradiation (photoCORM behavior). This journal is
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.
Organosulfide group transfer reactions of transition-metal carbonyl radicals: Electronic and steric effects
Lee, Kang-Wook,Brown, Theodore L.
, p. 1852 - 1856 (2008/10/08)
Photochemical reactions of M2(CO)10 (M = Mn, Re) with RSSR (R = Me, Ph) or MeSSiMe3 in hexane at ambient temperature yield (μ-SR)2M2(CO)8 (70-85%) and [M(CO)3SR]4 (0-15%). The corresponding reaction of Re2(CO)8L2 almost quantitatively yields (μ-SR)2Re2(CO)6L2, and the reaction of Re2(CO)10 and [Me2NC(S)S]2 gives (η2-S2CNMe2)Re(CO)4. The initial product for each reaction is RSM(CO)4L (L = CO, PR3), formed by RS group transfer from RSSR to the ?M(CO)4L radical generated by photolysis. (μ-SR)2M2(CO)8 is in equilibrium with the 16-electron species RSM(CO)4 under photochemical conditions. Laser flash photolysis kinetics studies reveal the electronic and steric effects of L ligands in the Re(CO)4L? radical and the steric effect of the R group in RSSR on the group transfer rate constant. The relative rate constants for reactions of Re(CO)4PMe3? with various dialkyl disulfides decrease in the order methyl > n-butyl > sec-butyl > tert-butyl (630:280:36:1). The rate constants for group transfer for a series of Re(CO)4L? radicals fit a two-parameter free energy relationship wherein the electronic and the steric parameters of L are represented. The reaction is accelerated by increased electron donor capability of L and retarded by increased size of L.
SYNTHESIS AND REACITVITY OF BRIDGING THIOLATO-MANGANESE CARBONYL COMPLEXES, Et4N
Treichel, P. M.,Tegen, M. H.
, p. 385 - 394 (2007/10/02)
The yellow-orange complexes Et4N (R= Ph, Me, t-Bu) have been prepared by several routes, including: (1) reactions of Et4N with Bu3SnSR; (2) reactions of Et4N with either Bu3SnSR, RSH, or NaSPh; and (3) reactions of Mn3(μ-X)2(CO)8 (X= Br, SPh) with NaSPh, followed by metathesis using Cl.The complex Et4Nt)3(C)6> can converted to EtnN by reaction with PhSH in the presence of either a base (pyridine) or an acid (CF3CO2H or CH3CO2H).These bridging thiolate complexes, Et4N undergo reactions with BF4 (or other electrophilic reagents) to give 4; if the same reactions are carried out in the presence of CO, Mn2(μ-SR)2(CO)8 is the product.Similarly, reactions of Et4N with BF4 in the presence of a phosphine (PMe3, dppm) produce the phosphine substituted species, cis-Mn2(μ-SR)2(CO)6(PMe3)2 and Mn2(μ-SR)2(CO)6(μ-dppm); the former is converted upon heating to the known species Mn2(μ-SR)2(μ-CO)(CO)4(PMe3)2.
