Bioorganometallic Chemistry: Reactions of Methyltitanocene Cation Complexes with a Singly Deprotected Methyl Glucopyranoside

Autor: Jutta Pyplo-Schnieders, Jens Müller, Hartmut Redlich, Birgit Meyer zu Berstenhorst, Gerhard Erker, Julia-Christina Wasilke, Gerald Kehr
Rok vydání: 2004
Předmět:
Zdroj: European Journal of Inorganic Chemistry. 2005:92-99
ISSN: 1099-0682
1434-1948
DOI: 10.1002/ejic.200400387
Popis: The dimethyltitanocene/B(C6F5)3 system reacts with the 4-unprotected methyl α-D-glucopyranoside derivative 5 (“HO-carb.”) to yield the ionic complex [Cp2Ti(O-carb.)]+[MeB(C6F5)3]− (10a). Spectroscopic studies have led us to believe that 10a is characterized by an internal ether-chelate structure in solution that involves coordination of the 6-OCH2Ph oxygen atom. Treatment of 10a with trimethylphosphane gives the open, non-chelated complex 11a, in which the phosphane coordinates to the metal center. Reaction of the THF-stabilized salt [Cp2TiCH3(THF)]+[BPh4]− (12a) with 5 gave complex 13a, with coordinated THF. Experiments with bis(methylcyclopentadienyl)titanium systems gave analogous results (complexes 10b, 11b and 13b). Zirconocenes react differently. Addition of dimethylzirconocene (14a) or dimethylbis(methylcyclopentadienyl)zirconium (14b) to 5 gave the neutral complexes 15a, 15b and methane. Treatment of 15a (15b) with B(C6F5)3 again resulted in the formation of an ionic chelate complex 16a (16b). A non-chelated complex 18 was formed by treating the THF-stabilized salt [Cp2ZrCH3(THF)]+[BPh4]− (17) with 5. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Databáze: OpenAIRE