To examine the effects of cyclopentadienyl and olefin substitution on preferred stereochemistry, a series of singly [SiMe2]-bridged ansa-niobocene and -tantalocene olefin hydride complexes has been prepared via reduction and alkylation of the corresponding dichloride complexes. In this manner, [Me2Si(η5-C5H4) (η5-C5H3-3-R)] M(CH2= CHR′)H (M = Nb, Ta; R = CHMe2, CMe3; R′ = H, C6H5; M = Ta; R = CHMe2, CMe3; R′ = Me), rac- and meso-[Me2-Si(η5-C5 H3-3-R)(η5-C5H3-3-R)]Nb (CH2= CH2)H (R = CMe3), and [Me2Si(η5-C5H2-2,4- (CHMe2)2)] Ta(CH2=CHR′)H (R′ = H, C6H5) have been prepared and characterized by NMR spectroscopy and, in some cases, X-ray diffraction. The doubly [SiMe2]-bridged ansa-tantalocene ethylene hydride complex [(1,2-SiMe2)2(η5-C5H-3,5- (CHMe2)2)(η5- C5H2-4-CMe3)]-Ta(CH2=CH2) H has been prepared from thermolysis of the methylidene methyl complex [(1,2-SiMe2)2(η5-C5H-3,5- (CHMe2)2)(η5-C5H2- 4-CMe3)]Ta(CH2)CH3. Addition of an excess of propylene or styrene to the tantalocene ethylene hydride results in olefin exchange and formation of the olefin hydride complexes [(1,2-SiMe2)2(η5-C5H-3,5- (CHMe2)2) (η5-C5H2-4-CMe3)]Ta (CH2=CHR′)H (R′ = CH3, C6H5). These compounds serve as stable transition state analogues for the much more kinetically labile group 4 metallocenium cationic intermediates in metallocene-catalyzed olefin polymerization. Characterization of the thermodynamically preferred isomers of metallocene olefin hydride complexes reveals that alkyl substitution on the cyclopentadienyl ligand array may have a significant effect on the stereochemistry of olefin coordination.
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry