Ring-methyl activation in pentamethylcyclopentadienyl complexes .7. Reactions of [Ru(eta(2):eta(5)-C5Me4CH2O(CH2)(n)CH=CHR2)(CO)(2)]+BF4(-) with nucleophilesстатья
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Аннотация:The ruthenium chelates containing tethered olefinic side chains [Ru(eta(2):eta(5)-C5Me4CH2O(CH2)(n)CH=CHR2)(CO)(2)]+BF4- (1a, R-2 = H, n = 1; 1b, R-2 = Me, n = 1; 1c, R-2 = H, n = 2) react with NaBH4 in MeOH or in water to give the non-chelated olefin hydride complexes [Ru(eta(5)-C5Me4CH2O(CH2)(n)CH = CHR2)(CO)(2)(H)] (2a-c). By contrast, allcoxide attacked at a carbonyl ligand in la giving the chelated olefin alkoxycarbonyl complexes [Ru(eta(2):eta(5)-C5Me4CH2OCH2CH=CH2)(eta(1)-COOR3)(CO)] (3a,a', R-3 = Me; 4a,a', R-3 = Et), which form a separable mixture of diastereomers. There was no evidence for attack at the coordinated olefin in complex 1. (C) 1997 Elsevier Science S.A.