SYNTHESIS OF ETA(5)-1,2,3,4,5-PENTAMETHYLCYCLOPENTADIENYL-PLATINUM COMPLEXESстатья
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Аннотация:Reaction of K2PtCl4 With pentamethylcyclopentadiene gave the exo-H isomer (1b, 25%) as well as the endo-H isomer (1a, 75%) of [pt(eta4-C5Me5H)Cl2]. The mixture reacted with AgBF4 in acetone at -78-degrees-C to give the mixed endo-H, exo-H isomeric dication solvate complexes [Pt(eta4-C5Me5H)(acetone)x]2+(BF4-)2 (2a,b), which decompose at room temperature to give [Pt(eta4-C5Me5H)(eta5-C5Me5)]+BF4- (3). The same reaction of 1a,b in the presence of dienes (pentamethylcyclopentadiene, cyclopentadiene, 1,3-cyclohexadiene, and 1,5-cyclooctadiene) occurs with spontaneous deprotonation to give the monocationic complexes, 3, [pt(eta4-C5Me5H)(eta5-C5Me5)]+BF4- (4a,b), [pt(eta4-C6H8)(eta5-C5Me5)]+BF4- (5), and [Pt(eta4-C8H12)(eta5-C5Me5)]+BF4- (6), respectively, in high yield. The products from the reaction depend on the ability of the coordinated diene to undergo deprotonation in an intermediate, in the order, eta4-1,3-cyclohexadiene approximately eta4-1,5-cyclooctadiene < eta4-endo-pentamethylcyclopentadiene < eta4-exo-pentamethylcyclopentadiene < eta4-cyclopentadiene. The solvent complexes [Mn(eta5-C5Me5)(acetone3]2+(BF4-)2 (M = Rh, Ir) react with C5Me5H to give decamethyl-rhodocenium and -iridocenium salts.