BARR, D and SNAITH, R and CLEGG, W and Mulvey, Robert and WADE, K (1987) The syntheses and crystal structures of two iminolithium adducts: (Ph2CNLi·NC5H5)4, a tetrameric pseudo-cubane formed by stacking two (LiN)2 four-membered rings, and [But2CNLi·OP(NMe2)3]2, a dimer prevented sterically from stacking. Journal of the Chemical Society, Dalton Transactions (9). pp. 2141-2147. ISSN 0300-9246Full text not available in this repository. (Request a copy from the Strathclyde author)
The syntheses and crystal structures of two iminolithium adducts [But2CNLi·OP(NMe2)3]2(1)[OP(NMe2)3= hexamethylphosphoramide (hmpa)] and (Ph2CNLi·NC5H5)4(2)(NC5H5= pyridine) are described. Adduct (1) contains a centrosymmetric planar (LiN)2 ring, with Li–N distances of 1.923(6) and 1.948(6)Å, and a ring angle at nitrogen of 75.4(3)°. Unexpectedly, the C2CN skeletal planes of its imino ligands are twisted 58.6(6)° with respect to the (LiN)2 ring plane, apparently to accommodate the bulky hmpa ligands, so preventing the (LiN)2 rings from stacking to form an (LiN)4 cubane structure. In contrast, adduct (2), with sterically compatible Ph2CN and NC5H5 ligands, has an (LiN)4 cubane structure with three distinct categories of metal–nitrogen distance (averaging 2.03,2.08, and 2.16 Å respectively) and ligand orientations that support an interpretation of this cubane in terms of two stacked (LiN)2 four-membered ring systems.
|Keywords:||tetrameric pseudo-cubane , dimer , crystal structures, Physical and theoretical chemistry|
|Subjects:||Science > Chemistry > Physical and theoretical chemistry|
|Department:||Faculty of Science > Pure and Applied Chemistry|
|Depositing user:||Pure Administrator|
|Date Deposited:||08 Feb 2012 16:00|
|Last modified:||05 May 2016 00:18|