NDLI: Rare-earth dichloro and bis(alkyl) complexes supported by bulky amido– imino ligand . Synthesis, structure, reactivity and catalytic activity in isoprene polymerization

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Cherkasov, Anton V. Trifonov, Alexander A. Fukin, Georgy K. Mahrova, Tatyana V. Lyubov, Dmitry M. Glukhova, Tatyana A. Kissel, Alexander A. Cui, Dongmei
Description	Author Affiliation: Kissel AA ( G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Nizhny Novgorod Tropinina str., 49, Russia.)
Abstract	A monoanionic amido– imino ligand system $[(2,6-iPr_{2}C_{6}H_{3})N=C(Me)C(=CH_{2})N(C_{6}H_{3}-2,6-iPr_{2})]^{−}$ was successfully employed for the synthesis of monomeric dichloro $[(2,6-iPr_{2}C_{6}H_{3})N=C(Me)C(=CH_{2})N(C_{6}H_{3}-2,6-iPr_{2})]LnCl_{2}(THF)_{2}$ (Ln = Y, 2Y; Lu, 2Lu) and bis(alkyl) $[(2,6-iPr_{2}C_{6}H_{3})N=C(Me)C(=CH_{2})N(C_{6}H_{3}-2,6-iPr_{2})]Ln(CH_{2}SiMe_{3})_{2}(THF)$ (Ln = Y, 4Y; Lu, 4Lu) species of yttrium and lutetium. Dichloro complexes 2Y and 2Lu turned out to be unstable in aromatic solvents . The ligand symmetrization reaction in the case of 2Y affords the yttrium complex coordinated by dianionic $[(2,6-iPr_{2}C_{6}H_{3})NC(=CH_{2})C(=CH_{2})N(C_{6}H_{3}-2,6-iPr_{2})]^{2−}$ ligand , $(2,6-iPr_{2}C_{6}H_{3})N=C(Me)C(Me)=N(C_{6}H_{3}-2,6-iPr_{2})$ and $YCl_{3}.$ On the contrary, bis(alkyl) species 4Y and 4Lu are rather stable and do not undergo such a transformation or thermal decomposition . The treatment of complex 4Y with DME resulted in C–O bond cleavage and the formation of a dimeric methoxy-alkyl species $\{[(2,6-iPr_{2}C_{6}H_{3})N=C(Me)C(=CH_{2})N(C_{6}H_{3}-2,6-iPr_{2})]Y(CH_{2}SiMe_{3})(μ-OMe)\}_{2}$ (5). The ternary systems $4Ln/AliBu_{3}/borate$ (borate = $[HNMe_{2}Ph][B(C_{6}F_{5})_{4}]$ and $[CPh_{3}][B(C_{6}F_{5})_{4}];$ molar ratio 1:10:1) performed high catalytic activity in isoprene polymerization and ability to convert into polymer 1000–5000 equivalents of isoprene in 20–120 min with quantitative conversion. The obtained polyisoprenes possessed high molecular weights (2.9 × $10^{4}–4.1$ × $10^{4})$ and moderate polydispersities (2.14–3.52). Predominant 3,4-regioselectivity (up to 78%) was observed.
ISSN	14779226
Issue Number	25
Volume Number	42
e-ISSN	13645447
Journal	Dalton Trans.
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2013-07-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Amides Chemistry Butadienes Hemiterpenes Imines Metals, Rare Earth Organometallic Compounds Chemical Synthesis Pentanes Catalysis Models, Molecular Molecular Structure Polymerization Journal Article Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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