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Lookup NU author(s): Dr Mark Elsegood, Professor William Clegg
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Several diorganoscandium complexes stabilized by the beta -diketiminato ligands (Ar)NC(R)CHC(R)N(Ar) (Ar = 2,6-iPr-C6H3; R = CH3 (ligand a), R = rBu (ligand b)) have been synthesized. Reaction of the lithium salts of the ligands with ScCl3. 3THF leads to the complexes LScCl2(THF)(n), which may be readily alkylated to form the dialkyl derivatives. Most are isolated as base-free, four-coordinate complexes. Several have been characterized via X-ray crystallography, and a detailed discussion of their structures is presented. Steric interactions between Ar and the Sc-alkyl groups force the scandium to adopt an out-of-plane bonding mode. In solution, this is manifested via a fluxional process which equilibrates the two diastereotopic alkyl groups and ligand groups as well. The barriers to this process roughly correlate with the steric bulk of the alkyl substituents. At elevated temperatures, the dialkyl derivatives LScR2 undergo a metalation process whereby one of the alkyl groups is eliminated as RH, and a ligand iPr group is metalated in the methyl position. These reactions are first order in scandium complex, and activation parameters of DeltaH(double dagger) = 19.7(6) kcal mol(-1) and DeltaS(double dagger) = -17(2) cal mol(-1) K-1 were measured for the loss of Me4Si from (Ligb)Sc(CH2SiMe3)(2).
Author(s): Hayes PG, Piers WE, Lee LWM, Knight LK, Parvez M, Elsegood MRJ, Clegg W
Publication type: Article
Publication status: Published
Journal: Organometallics
Year: 2001
Volume: 20
Issue: 12
Pages: 2533–2544
ISSN (print): 0276-7333
ISSN (electronic): 1520-6041
Publisher: American Chemical Society
URL: http://dx.doi.org/10.1021/om010131o
DOI: 10.1021/om010131o
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