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• W1968171191 abstract "Abstract The protonolysis reaction of [Ln(AlMe 4 ) 3 ] with various substituted cyclopentadienyl derivatives HCp R gives access to a series of half‐sandwich complexes [Ln(AlMe 4 ) 2 (Cp R )]. Whereas bis(tetramethylaluminate) complexes with [1,3‐(Me 3 Si) 2 C 5 H 3 ] and [C 5 Me 4 SiMe 3 ] ancillary ligands form easily at ambient temperature for the entire Ln III cation size range (Ln=Lu, Y, Sm, Nd, La), exchange with the less reactive [1,2,4‐(Me 3 C) 3 C 5 H 3 ] was only obtained at elevated temperatures and for the larger metal centers Sm, Nd, and La. X‐ray structure analyses of seven representative complexes of the type [Ln(AlMe 4 ) 2 (Cp R )] reveal a similar distinct [AlMe 4 ] coordination (one η 2 , one bent η 2 ). Treatment with Me 2 AlCl leads to [AlMe 4 ] → [Cl] exchange and, depending on the Al/Ln ratio and the Cp R ligand, varying amounts of partially and fully exchanged products [{Ln(AlMe 4 )(μ‐Cl)(Cp R )} 2 ] and [{Ln(μ‐Cl) 2 (Cp R )} n ], respectively, have been identified. Complexes [{Y(AlMe 4 )(μ‐Cl)(C 5 Me 4 SiMe 3 )} 2 ] and [{Nd(AlMe 4 )(μ‐Cl){1,2,4‐(Me 3 C) 3 C 5 H 2 }} 2 ] have been characterized by X‐ray structure analysis. All of the chlorinated half‐sandwich complexes are inactive in isoprene polymerization. However, activation of the complexes [Ln(AlMe 4 ) 2 (Cp R )] with boron‐containing cocatalysts, such as [Ph 3 C][B(C 6 F 5 ) 4 ], [PhNMe 2 H][B(C 6 F 5 ) 4 ], or B(C 6 F 5 ) 3 , produces initiators for the fabrication of trans ‐1,4‐polyisoprene. The choice of rare‐earth metal cation size, Cp R ancillary ligand, and type of boron cocatalyst crucially affects the polymerization performance, including activity, catalyst efficiency, living character, and polymer stereoregularity. The highest stereoselectivities were observed for the precatalyst/cocatalyst systems [La(AlMe 4 ) 2 (C 5 Me 4 SiMe 3 )]/B(C 6 F 5 ) 3 ( trans ‐1,4 content: 95.6 %, M w / M n =1.26) and [La(AlMe 4 ) 2 (C 5 Me 5 )]/B(C 6 F 5 ) 3 ( trans ‐1,4 content: 99.5 %, M w / M n =1.18)." @default.
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• W1968171191 date "2008-08-06" @default.
• W1968171191 modified "2023-10-18" @default.
• W1968171191 title "Half-Sandwich Bis(tetramethylaluminate) Complexes of the Rare-Earth Metals: Synthesis, Structural Chemistry, and Performance in Isoprene Polymerization" @default.
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• W1968171191 doi "https://doi.org/10.1002/chem.200800492" @default.
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