Isomerization, reactivity, and structural study of a thioperoxide-bridged dimolybdenum(V) dimer
نویسندگان
چکیده
Isomerization, Reactivity, and Structural study of a Thioperoxide-bridged Dimolybdenum(V) Dimer Chi Minh Tuong April 8, 2004 The synthesis of the methyl thioperoxide-bridged dimolybdenum(V) dimer, structurally characterized by crystallography. The compound proved to be very stable to light and heat. The possibility of photolytic or thermolytic rearrangement of the methyl thioperoxide ligand (u-S-O-R) to a methyl sulfinylligand (u-S(=O)R) was investigated. These studies showed that the methyl thioperoxide compound did not produce the desired sulfinyl isomer. The photolyses produced mainly a derivative of the methyl thioperoxide compound, where a hydroxo bridge is thought to have replaced the acetate bridge. Minor products formed in general agreement with the photolysis chemistry of organic sulfenate esters (R'S-OR). The thermolyses cleaved the s-o bond, led to an intramolecular reaction and to some decomposition. in the protonation of the s-o bond's oxygen and the synthesis of a new compound,
منابع مشابه
Preparation and reactivity of a dinitrogen-bridged dimolybdenum-tetrachloride complex.
A dinitrogen-bridged dimolybdenum-tetrachloride complex is prepared and reduced with Super-Hydride (LiBHEt3) to afford the corresponding dimolybdenum-dinitrogen complex together with the formation of molecular dihydrogen. This reaction proceeds via the ligand exchange of the coordinated dihydrogen generated in situ with molecular dinitrogen.
متن کاملUnique behaviour of dinitrogen-bridged dimolybdenum complexes bearing pincer ligand towards catalytic formation of ammonia
It is vital to design effective nitrogen fixation systems that operate under mild conditions, and to this end we recently reported an example of the catalytic formation of ammonia using a dinitrogen-bridged dimolybdenum complex bearing a pincer ligand, where up to twenty three equivalents of ammonia were produced based on the catalyst. Here we study the origin of the catalytic behaviour of the ...
متن کاملMode-specific fragmentation of amino acid-containing clusters.
A combination of infrared multiple photon dissociation (IRMPD) spectroscopy and density functional theory calculations have been employed to study the structures and mode-specific dissociation pathways of the proton-bound dimer of 3-trifluoromethylphenylalanine (3-CF3-Phe) and trimethylamine (TMA). Three structural motifs are identified: canonical (charge-solvated), zwitterionic (charge-separat...
متن کاملDivergent Reactivity of a Dinuclear (NHC)Nickel(I) Catalyst versus Nickel(0) Enables Chemoselective Trifluoromethylselenolation
We herein showcase the ability of NHC-coordinated dinuclear NiI -NiI complexes to override fundamental reactivity limits of mononuclear (NHC)Ni0 catalysts in cross-couplings. This is demonstrated with the development of a chemoselective trifluoromethylselenolation of aryl iodides catalyzed by a NiI dimer. A novel SeCF3 -bridged NiI dimer was isolated and shown to selectively react with Ar-I bon...
متن کاملBase Catalyzed Cyclization and Isomerization of 3-Propargylmercapto-1, 2,4-Triazine to Thiazolo [3,2-b][1,2,4]-Triazines
Transformation of 3-propargylmercapto-6 methyl-1, 2,4-triazin- 5 (2H)- one (1; R=CH3) to 3,6- dimethyl-7H- thiazolo [3,2-b] [1, 2, 4] triazin -7- one (2) is performed under basic condition. The formation of (2) may be mainly due to the high reactivity of acetylenes towards nucleophiles and isomerization of the intermediate.
متن کامل