Cocondensation reactions of nitrogen-containing heterocycles with lithium atoms at 77 K

Synthetic Techniques and Applications of Activated Nanostructurized Metals: Highlights up to 2008

“…Nowadays, cryochemical procedures are applied for obtaining metal-polymer materials (by low-temperature cocondensation of metal and monomer vapors followed by low-temperature solid-state polymerization of the cocondensate under irradiation) [42][43][44][45] and various metal complexes, for instance isomeric complexes [Ni( 3 -PC 2 Bu t 2 )( 5 -P 3 C 2 t Bu 2 )] and [Ni( 4 -P 2 C 2 Bu t 2 ) 2 ] (by the reaction of nickel atoms with t BuCP) [46], In(P 3 C 2 Bu' 2 ) [47], zerovalent bis( -arene)lanthanide complexes of the form [Ln( 6 -C 6 H 3 -t Bu 3 -1,3,5) 2 ] (by codeposition of a monatomic lanthanide vapor (Sm, Eu, Tm or Yb) and tri-tert-butylbenzene C 6 H 3 -t Bu 3 -1,3,5 onto a cold (77 K) surface) [48], and others [49][50][51]. Low temperature surface chemistry and nanostructures are reviewed in [52].…”

Cocondensation reactions of heterocyclic aromatic compounds with lithium, calcium and magnesium atoms at 77K

“…The work has been expanded to +I substituted (CMe 3 , SiMe 3 , o-and m-xylene) and donor substituted (OMe, NMe 2 , SMe) benzene derivatives [7] as well as five-membered heterocycles [8] and nitrogen-containing heterocycles [9]. In the case of anisole a selective C-H bond activation was found to occur in the absence of THF as well; its reaction mechanism was calculated in detail in a recent DFT study [10].…”

“…Earlier reports showed that lithium atoms are able to [9] dimerise pyridine molecules (9) by losing hydrogen in the para-position. When lithium atoms were cocondensed with pyridine in a THF solution, the reaction lead to a non-lithiated species.…”