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  • Title: Racemic N-aryl bis(amidines) and bis(amidinates): on the trail of enantioselective organolanthanide catalysts.
    Author: Hill MS, Hitchcock PB, Mansell SM.
    Journal: Dalton Trans; 2006 Mar 28; (12):1544-53. PubMed ID: 16538273.
    Abstract:
    A series of racemic N-aryl-substituted trans-1,2-diaminocyclohexyl (t-1,2-DACH)-linked bis(amidines) were synthesised and their solution behaviour, and solid-state structures were investigated. The amidine functionalities within these compounds were extremely sterically hindered, with ortho-aryl substitution found to hinder N-Ar bond rotation. The results of these studies were used to rationalise the lack of reactivity of these compounds with [Y{N(SiMe(3))(2)}(3)]. Dilithiation of the t-1,2-DACH linked bis(amidines) did, however, proceed easily and the solution behaviour and solid-state structures of the resulting THF-solvated lithium amidinates were investigated. All the compounds showed similar structures in the solid-state, while NMR experiments indicated that the solid-state structures were likely to be maintained in solution. Attempted metathesis reactions with YCl(3) did not, however, yield the desired yttrium chloride complexes.
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