A solid state and theoretical study of the solvent effects controlling the mono- and di-lithiation of aromatic primary amines
- 21 May 2002
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 12,p. 2505-2511
- https://doi.org/10.1039/b107970k
Abstract
Reaction of 1-naphthylamine, 4-tritylaniline or 4-methylaniline with two equivalents of BunLi in Et2O or thf affords rare geminal N,N-dilithiates of general formula (L)n·(Li2NAr)10 (L = Et2O, n = 6, Ar = 1-C10H71, C6H4-4-CPh32; L = thf, n = 10, Ar = C6H4-4-Me 3). X-Ray crystal structure analyses reveal that the core (Li14N10)6− frameworks consist of two fused rhombic dodecahedra. Ab initio M.O. calculations on the mono- and di-lithiation of 1-naphthylamine and 4-methylaniline suggest that the selectivity with which polymetallation occurs is solvent dependent and so help to rationalise the experimentally observed structures.Keywords
This publication has 51 references indexed in Scilit:
- Crystal Structure of Dilithioacetylacetone: A Twenty‐Four Vertex Li‐O Cage Molecule with Limited Li–C(terminal) Bonding and Selective THF SolvationAngewandte Chemie International Edition in English, 1995
- Dilithiated salen complexes: chiral [(salen)Li2·hmpa]2and deliberate partial hydrolysis to give [(salen)Li2]3·Li2O·2tmen·H2O [H2salen =N,N′-ethylenebis(salicylideneimine); hmpa = hexamethylphosphoramide; tmen = tetramethylethylenediamine]Journal of the Chemical Society, Chemical Communications, 1995
- Lithium anilide complexed by pmdeta: expectation of a simple monomer, but in reality an odd trinuclear composition combining three-, four- and five-coordinate lithiumJournal of the Chemical Society, Chemical Communications, 1995
- Ladder structures in lithium amide chemistry: syntheses, solid-state, and solution structures of donor-deficient lithium pyrrolidide complexes, [cyclic] {[H2C(CH2)3NLi]3.cntdot.PMDETA}2 and [cyclic] {[H2C(CH2)3NLi]2.cntdot.TMEDA}2, and ab initio MO calculations probing ring vs ladder vs stack structural preferencesJournal of the American Chemical Society, 1989
- Structure and reactivity of lithium amides. Lithium-6, carbon-13, and nitrogen-15 NMR spectroscopic studies and colligative measurements of lithium diphenylamide and lithium diphenylamide-lithium bromide complex solvated by tetrahydrofuranJournal of the American Chemical Society, 1988
- Structures of the lithium salts of aromatic secondary amines in weakly polar aprotic solventsJournal of the American Chemical Society, 1987
- Synthesis of α-lithioarylmethanes of m-xylene and its α-trimethylsilyl derivatives; crystal structure of [{Li(Me2NCH2CH2NMe2)}2{C6H4(CHSiMe3)2-m}]J. Chem. Soc., Dalton Trans., 1985
- Metal secondary amides derived from the highly hindered 2,4,6-tri-t-butylaniline; X-ray crystal structure of trans-[Li(µ-NHAr)(OEt2)]2(Ar = C6H2But3-2,4,6)Journal of the Chemical Society, Chemical Communications, 1984
- X-Ray crystal structure of [{o-C6H4(CHPh)2}{Li(tmeda)}2](tmedaMe2NCH2CH2NMe2). Unsymmetrical lithium bridging and (E,E)-conformation of the phenyl groupsJournal of the Chemical Society, Chemical Communications, 1984
- Unusual molecular structures of some sterically hindered lithium amides: electron diffraction results on gaseous [Li{N(SiMe3)2}]2 and X-ray data on crystalline monomeric Li(NHAr)(tmeda)(Ar = C6H2But 3-2,4,6; tmeda = Me2NCH2CH2NMe2)Journal of the Chemical Society, Chemical Communications, 1984