602335-55-7Relevant academic research and scientific papers
Selective halodemethylation reactions of metallocene dimethyls with triphenylmethyl chloride and benzyl bromide
Hawrelak, Eric J.,Deck, Paul A.
, p. 9 - 11 (2008/10/09)
NMR-scale reactions of several group 4 metallocene dimethyls with either trityl chloride or benzyl bromide gave the corresponding L2M(Me)X complexes selectively. Five reactions, including syntheses of Cp2-Zr(Me)Cl and Ind2Zr(Me)Cl, were conducted on a preparative scale to afford useful isolated yields of L2M-(Me)Cl complexes.
Analysis of metallocene-methylalumoxane methide transfer processes in solution using a 19F NMR spectroscopic probe
Hawrelak, Eric J.,Deck, Paul A.
, p. 3558 - 3565 (2008/10/08)
The metallocenes (C6F5C5H 4)CpZrMe2 (1, Cp = C5H5) and (C 6F5C5H4)2MMe2 (2a, M = Zr; 2b, M = Hf) were treated with B(C6F5) 3 and, separately, with commercial methylalumoxane (MAO, depleted of excess Me3Al). The ensuing methide transfer reactions were followed by 19F NMR. Spectra of the activated species obtained using MAO and excess B(C6F5)3 were strikingly similar, suggesting that similar cation-like species are formed using either organo-Lewis acid, and the MAO-activated species were tentatively formulated as (C6F5C5H4CpZrMe+ Me[AlMeO]n- and as (C6F5C 5H4)2MMe+ Me[AlMeO]n - (M = Zr, Hf). The relative amount of L2MMe2 and [L2MMe]+ species observed in solution was measured as a function of [MAO] and as a function of [M] at constant [MAO]. Results are interpreted in terms of a canonical model in which MAO contains relatively few highly active Lewis acidic sites.
