Ring-methyl activation in pentamethylcyclopentadienyl complexes 7 reactions of [Ru(η2:η5-C5Me4CH2O(CH2)nCH=CHR2)(CO)2]+BF4ȡ with nucleophiles

The ruthenium chelates containing tethered olefinic side chains [Ru(η2:η5-C5Me4CH2O(CH2)nCH=CHR2)(CO)2]+BF4ȡ (1a, R2 = H, n = 1; 1b, R2 = Me, n = 1; 1c, R2 = H, n = 2) react with NaBH4 in MeOH or in water to give the non-chelated olefin hydride complexes [Ru(η5-C5Me4CH2O(CH2)nCH=CHR2)(CO)2(H)] (2aȁc...

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Bibliographic Details
Published in:Journal of organometallic chemistry 1997-05, Vol.536-537, p.191-196
Main Authors: Gusev, Oleg V., Morozova, Larisa N., Peganova, Tat'ayana A., Antipin, Mikhail Yu, Lyssenko, Konstantin A., Noels, Alfred F., O'Leary, Shane R., Maitlis, Peter M.
Format: Article
Language:English
Subjects:
Crystal structure
Cyclopentadienyl
Nucleophilic attack
Olefin chelate
Ruthenium
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Summary:The ruthenium chelates containing tethered olefinic side chains [Ru(η2:η5-C5Me4CH2O(CH2)nCH=CHR2)(CO)2]+BF4ȡ (1a, R2 = H, n = 1; 1b, R2 = Me, n = 1; 1c, R2 = H, n = 2) react with NaBH4 in MeOH or in water to give the non-chelated olefin hydride complexes [Ru(η5-C5Me4CH2O(CH2)nCH=CHR2)(CO)2(H)] (2aȁc). By contrast, alkoxide attacked at a carbonyl ligand in 1a giving the chelated olefin alkoxycarbonyl complexes [Ru(η2:η5-C5Me4CH2OCH2CH=CH2)(η1-COOR3)(CO)](3a,aȃ, R3 = Me; 4a,aȃ, R3 = Et), which form a separable mixture of diastereomers. There was no evidence for attack at the coordinated olefin in complex 1.
ISSN:0022-328X
1872-8561
DOI:10.1016/S0022-328X(96)06715-0