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The synthesis and structure of lithium derivatives of the sterically encumbered β-diketiminate ligand [{(2,6-Pri2H3C6)N(CH3)C}2CH]–, and a modified synthesis of the aminoimine precursor

2001; Royal Society of Chemistry; Issue: 23 Linguagem: Inglês

10.1039/b103149j

1472-7773

Matthias Stender, Robert Wright, Barrett E. Eichler, J. Prust, Marilyn M. Olmstead, Herbert W. Roesky, Philip P. Power,

Synthesis and characterization of novel inorganic/organometallic compounds

The reaction of the β-aminoimine compound (2,6-Pri2H3C6)NC(CH3)CHC(CH3)N(C6H3-2,6-Pri2)H (1, Dipp2nacnacH; Dipp = C6H3-2,6-Pri2) with n-BuLi in diethyl ether or tetrahydrofuran afforded the solvates Dipp2nacnacLi(Et2O) (2) and Dipp2nacnacLi(THF) (3), respectively, which crystallized as monomers featuring the Li+ ions in a distorted trigonal planar environment and an essentially planar arrangement for the LiN2C3 ring. The lithiation of 1, in the absence of a donor solvent, afforded a Dipp2nacnacLi product that crystallized in two different types of associated structures, 4a and 4b. In the dimer 4a, the Li+ ion is coordinated to the two nitrogens of the Dipp2nacnac ligand, and it is associated by coordination of lithium to a carbon of the Dipp ring of the other Dipp2nacnac unit of the dimer. In the dodecamer 4b, the asymmetric unit consists of a chain of six LiDipp2nacnac units associated by interactions of the Li+ ions with one or two carbons from a Dipp ring of the next molecule in the chain. The hexamer is linked to an identical one (generated through an inversion center) by Li+–Dipp interactions involving the first and third lithium atoms from each hexamer, thereby generating an overall dodecameric structure of a type that was previously unknown for lithium salts. An improved yield synthesis for 1 was also developed.