Tris methane, reaction with complexes

Catalytic transformations involving the C-H bonds of thiophene are rare, but recently there has been a report on the catalytic addition of the C(2)-H bond of thiophene across ethylene to form 2-ethylthiophene <20040M5514>. Reaction of the ruthenium complex TpRu(CO)(NCMe)(Me) (where Tp = hydrido tris(pyrazolyl)borate) with thiophene produces the 2-thienyl complex 249 and methane. This complex catalyzes the formation of 2-ethylthiophene from a solution of thiophene and ethylene (Equation 121). The mechanism of this reaction has been explored. 

Smith and Raymond (1985) produced a hexaazacyclohexadecane by reacting tris(aminoethyl)amine with bis(methylamino)methane in the presence of La(III). The bis(methylamino)methane was the source of the methylene group in the macrocycle. The La(III) complex prepared in this reaction is 10-... 

Selective mesylation of methyl a-o-glucopyranoside using 3.1 moles of methane sulphonyl chloride gave predominantly the 2,4,6-tri-O-mesylate whereas under the same conditions toluene-p-sulphonyl chloride gave mainly the 2,6-di-O-tosyl derivative together with approximately equal amounts of the 2,3,6- and 2,4,6-tri-O-tosyl derivatives. The reaction with p-bromobenzene sulphonyl chloride gave an unresolved complex mixture of products. ... 

A rather complex mixture of products is obtained from the reaction of benzyl-idenetriphenylphosphorane and CS2.48 The major product from the reaction of diphenyl disulphide with methylenetriphenylphosphorane is tris(phenylthio)-methane (44) and only a trace of the insertion product bis(phenylthio)methane is isolated.49 Presumably the salt (45) is deprotonated before it can react with the phenylthioate anion (Scheme 12). a-Thiocarbonyl-stabilized ylides (46) are obtained from the reaction of ylides with S-alkyl thiolcarboxylates.50... 

The vapor-phase pyrolysis of 4-hydroxy-1,2,3-triazole and its iV-methyl derivative affords methan-imine and its A-methyl analog. Analysis of the reaction path by the MNDO method shows the presence of two stable or metastable isomers, (liif)-4-hydroxy-l,2,3-triazole and its ketone protomer <89NJC551>. 4-Diazo-1,2,3-triazoles (122) thermolyze or photolyze in benzene to 4//-l,2,3-tri-azolylidenes (123) which convert benzene to 4-phenyl-1,2,3-triazoles and/or isomerize to a-diazo-nitriles (124). Intermediates (124) react with benzene via a carbene to give addition, ring expansion or substitution products (Scheme 17) <82TL5115>. The similar thermolysis of diazotriazoles in substituted benzene gives complex mixtures in which all of the components are sometimes impossible to isolate and identify <90AHC(48)65>. 

Reaction of the bis(diphenylphosphino)methane (dppm) complex PdPt-(yi-dppm)2Cl2 (132) with carbonylate anions affords several tri- and tetranuclear clusters. Reactions are outlined in Scheme 7. Treatment of 132 with 2 mol equivalents of [Fe(CO)3(NO)] (796,797), [Co(CO)4] (196,198), or [Mn(CO)5] (196,197) results in the tetranuclear spiked triangular clusters 133,134, or 135. Crystal structures on the dipalladium analogues of 134 and 135 have been reported (797,799). Grossel et al. (136) and Braunstein et al. (200) have independently reported that reaction of 132 with 1 mol equivalent of [Fe(CO)4]2 at ambient temperatures leads to an inseparable 1 1 mixture... 

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