Distinct C−H Bond Activation Pathways in Diamido-Pyridine-Supported Rare-Earth Metal Hydrocarbyl Complexes

2007 ◽  
Vol 26 (24) ◽  
pp. 6029-6041 ◽  
Author(s):  
Melanie Zimmermann ◽  
Frank Estler ◽  
Eberhardt Herdtweck ◽  
Karl W. Törnroos ◽  
Reiner Anwander
Keyword(s):  
Rare Earth ◽  
Rare Earth Metal ◽  
Bond Activation ◽  
Earth Metal ◽  
Activation Pathways

C–H bond activation of N-heterocyclic carbene IMes by rare-earth metal alkyl complexes

2010 ◽  
Vol 695 (25-26) ◽  
pp. 2794-2797 ◽  
Author(s):  
Waldemar Fegler ◽  
Teruhiko Saito ◽  
Kazushi Mashima ◽  
Thomas P. Spaniol ◽  
Jun Okuda
Keyword(s):  
Rare Earth ◽  
Rare Earth Metal ◽  
Bond Activation ◽  
Earth Metal ◽  
Alkyl Complexes

Rare-earth metal-promoted (double) C–H-bond activation of a lutidinyl-functionalized alkoxy ligand: formation of [ONC] pincer-type ligands and implications for isoprene polymerization

2020 ◽  
Vol 49 (6) ◽  
pp. 2004-2013 ◽  
Author(s):  
Dominic Diether ◽  
Melanie Meermann-Zimmermann ◽  
Karl W. Törnroos ◽  
Cäcilia Maichle-Mössmer ◽  
Reiner Anwander
Keyword(s):  
Rare Earth ◽  
Rare Earth Metal ◽  
Bond Activation ◽  
Earth Metal ◽  
Isoprene Polymerization

Steric pressure enforces the formation of dianionic and trianionic pincer-type ligands involving a rare alkylidene moiety in the latter case.

C–H Bond Activation and Isoprene Polymerization by Rare-Earth-Metal Tetramethylaluminate Complexes Bearing Formamidinato N-Ancillary Ligands

2013 ◽  
Vol 32 (5) ◽  
pp. 1209-1223 ◽  
Author(s):  
Shima Hamidi ◽  
Lars N. Jende ◽  
H. Martin Dietrich ◽  
Cäcilia Maichle-Mössmer ◽  
Karl W. Törnroos ◽  
...  
Keyword(s):  
Rare Earth ◽  
Rare Earth Metal ◽  
Bond Activation ◽  
Earth Metal ◽  
Ancillary Ligands ◽  
Isoprene Polymerization

scholarly journals Reactivity of halfsandwich rare-earth metal methylaluminates toward potassium (2,4,6-tri-tert-butylphenyl)amide and 1-adamantylamine

2015 ◽  
Vol 39 (10) ◽  
pp. 7640-7648 ◽  
Author(s):  
Dorothea Schädle ◽  
Markus Enders ◽  
Christoph Schädle ◽  
Cäcilia Maichle-Mössmer ◽  
Karl W. Törnroos ◽  
...  
Keyword(s):  
Rare Earth ◽  
Rare Earth Metal ◽  
Bond Activation ◽  
Earth Metal ◽  
Exchange Reactions

Donor functionalities drastically affect salt-metathetical methylaluminato–amido exchange reactions in CpRLn(AlMe4)2 by triggering methylaluminate cleavage and C–H bond activation of proximal aliphatic groups.

scholarly journals C–H-Bond Activation and Isoprene Polymerization Studies Applying Pentamethylcyclopentadienyl-Supported Rare-Earth-Metal Bis(Tetramethylaluminate) and Dimethyl Complexes

Molecules ◽  
2019 ◽  
Vol 24 (20) ◽  
pp. 3703 ◽  
Author(s):  
Christoph O. Hollfelder ◽  
Melanie Meermann-Zimmermann ◽  
Georgios Spiridopoulos ◽  
Daniel Werner ◽  
Karl W. Törnroos ◽  
...  
Keyword(s):  
Rare Earth ◽  
Rare Earth Metal ◽  
Binary Systems ◽  
Bond Activation ◽  
Earth Metal ◽  
Active Species ◽  
Redistribution Reactions ◽  
Butadiene Polymerization ◽  
Directing Effect ◽  
Half Sandwich

As previously shown for lutetium and yttrium, 1,2,3,4,5-pentamethylcyclopentadienyl (C5Me5 = Cp*)-bearing rare-earth metal dimethyl half-sandwich complexes [Cp*LnMe2]3 are now also accessible for holmium, dysprosium, and terbium via tetramethylaluminato cleavage of [Cp*Ln(AlMe4)2] with diethyl ether (Ho, Dy) and tert-butyl methyl ether (TBME) (Tb). C–H-bond activation and ligand redistribution reactions are observed in case of terbium and are dominant for the next larger-sized gadolinium, as evidenced by the formation of mixed methyl/methylidene clusters [(Cp*Ln)5(CH2)(Me)8] and metallocene dimers [Cp*2Ln(AlMe4)]2 (Ln = Tb, Gd). Applying TBME as a “cleaving” reagent can result in both TBME deprotonation and ether cleavage, as shown for the formation of the 24-membered macrocycle [(Cp*Gd)2(Me)(CH2OtBu)2(AlMe4)]4 or monolanthanum complex [Cp*La(AlMe4){Me3Al(CH2)OtBu}] and monoyttrium complex [Cp*Y(AlMe4)(Me3AlOtBu)], respectively. Complexes [Cp*Ln(AlMe4)2] (Ln = Ho, Dy, Tb, Gd) and [Cp*LnMe2]3 (Ln = Ho, Dy) are applied in isoprene and 1,3-butadiene polymerization, upon activation with borates [Ph3C][B(C6F5)4] and [PhNHMe2][B(C6F5)4], as well as borane B(C6F5)3. The trans-directing effect of AlMe3 in the binary systems [Cp*Ln(AlMe4)2]/borate is revealed and further corroborated by the fabrication of high-cis-1,4 polybutadiene (97%) with “aluminum-free” [Cp*DyMe2]3/[Ph3C][B(C6F5)4]. The formation of multimetallic active species is supported by the polymerization activity of pre-isolated cluster [(Cp*Ho)3Me4(CH2)(thf)2].

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