Synthesis, characterization, and reactivity of lanthanide complexes with bulky silylallyl ligands

Woodman, Timothy J., Schormann, Mark and Bochmann, Manfred (2003) Synthesis, characterization, and reactivity of lanthanide complexes with bulky silylallyl ligands. Israel Journal of Chemistry, 42 (4). pp. 283-293. ISSN 1869-5868

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Abstract

The synthesis of new lanthanide allyl complexes of enhanced stability and solubility in saturated hydrocarbons based on silyl-substituted allyl ligands is reported. Thus the potassium salt K(CH2CHCHSiMe3) ( 1 ) reacts with YCl3 in tetrahydrofuran to give the tris-allyl complex Y(CH2CHCHSiMe3)3 ( 2 ), while K(CH2CHCHSiMe2tBu) ( 3 ) affords Y(CH2CHCHSiMe2tBu)3(THF)1.5 ( 4 ). Slow re-crystallization of 4 from light petroleum in the presence of tert-butylcyanide led to multiple insertion to give the sec-amido complex Y{NHC(tBu)(CH)3SiMe2tBu}2{?2-NHC(tBu)CH=CHCH2SiMe2tBu)CH(CHCHSiMe2tBu)CtBuNH}(THF)·(CH3CH(Me)(CH2)2CH3) ( 5 ), which was crystallographically characterized. The reaction of ScCl3(THF)3 with two equivalents of Li{1,3-C3H3(SiMe3)2} in tetrahydrofuran gives the bis-allyl complex {1,3-C3H3(SiMe3)2}2Sc(µ-Cl)2Li(THF)2 ( 6 ), while the analogous reaction of K{1,3-C3H3(SiMe3)2} ( 7 ) with either LaCl3 or YCl3 in tetrahydrofuran affords the bis-allyl complexes MCl{1,3-C3H3(SiMe3)2}2(THF)x (8, M = La, x = 1; 9, M = Y, x = 0). An attempt to prepare the similar neodymium complex gave the mono-allyl complex NdI2{1,3-C3H3(SiMe3)2}(THF)1.25 ( 10 ). The reactions of 8 and 9 with triisobutyl aluminum in benzene-d6 show allyl exchange between lanthanide and aluminum. Complexes 8 , 9 , and 10 have been tested with a variety of activator systems as catalysts for the polymerization of 1,3-butadiene.

Item Type:	Article
Faculty \ School:	Faculty of Science > School of Chemistry (former - to 2024)
UEA Research Groups:	Faculty of Science > Research Groups > Chemistry of Materials and Catalysis Faculty of Science > Research Groups > Chemistry of Light and Energy Faculty of Science > Research Groups > Synthetic Chemistry (former - to 2017)
Depositing User:	Rachel Smith
Date Deposited:	02 Nov 2010 17:48
Last Modified:	06 Feb 2025 03:31
URI:	https://ueaeprints.uea.ac.uk/id/eprint/10488
DOI:	10.1560/JL3X-DXE1-CD6R-FCB0

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