Molybdenum cyclopentadienyl tricarbonyl derivatives

A. Chaloyard and N. El Murr, Inorg. Chem., 1980, 19, 3217. Synthesis of ring-substituted derivatives of cyclopentadienyl tricarbonyl complexes of molybdenum and tungsten. 

Similarly, acetylene itself gave ferrocene. Cyclopentadienyl(methyl)molybdenum tricarbonyl reacted with diphenylacetylene to produce some tetraphenylcyclopentadiene. The corresponding ethylmolybdenum derivative gave some tetraphenyl-methylcyclopentadiene. The cyclizations involved in these reactions and the trimethylchromium reaction above are quite unusual and certainly deserve further study. 

Treatment of Cp"Cr(Ti -Cot), Cp" = Cp, Cp with (EtCN)3M(CO)3, M = Mo, W and Fe2(CO)9 affords the complexes [(Cp Cr)(CO)3M][ i-Cot], M = Fe, Cr, W, Cp = Cp and I(Cp Cr)(CO)3Crl/i-Cot, Cot = Cyclooctatetrane, which have been spectroscopically characterised. Bimetallic complexes containing bis(tetramethylcyclopentadienyl) dimethylsilane bridges have been prepared from the reaction of arene tricarbonyl molybdenum complexes with the silyl substituted cyclopentadienyl derivative. The synthesis of pinanylcyclopentadienes followed by metallation and reaction with Mo(CO)s and Mel gives the chiral (-)-[(ii -C5Me4-3-pinanyl)(CO)3Me], which has been structurally characterised. The chiral methallyl complexes CpMo(NO)X(Ti -2-methallyl) X = camphorsulfonate have been resolved and the reactions of the... 

Reactions of thioketones with nucleophilic reagents have been studied to some extent. Thiobenzophenone (20) and its 4,4 -substituted derivatives react with cyclopentadienyliron dicarbonyl anion and cyclopentadienyl-molybdenum or -tungsten tricarbonyl anion at room temperature to give fulvenes. Phase-transfer catalysis conditions improve the yields. An electron-transfer mechanism has been proposed for this desulphurization and coupling reaction. An electron-transfer mechanism has also been proposed for the reduction of thiopivalophenone (54) by 1-benzyl-1,4-dihydronicotinamide in acetonitrile. 2,3-Diphenylcyclopropene-thione (55) reacts with 7V-methylarylamines to give the bicyclic thioamides (56). The formation of a thioketen as an intermediate has been suggested. A similar reaction scheme has also been proposed for the reaction of (55) with 3,4-dihydroisoquinoline. ... 

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