Azomethine derivatives. Part V. Reactions between organolithium compounds and diphenylketimine, some cyanides, and NNN′N′-tetramethylguanidine

Abstract

Reactions in ether between methyl-lithium and diphenylketimine, or between phenyl-lithium and phenyl cyanide, give a red solution of diphenylketiminolithium, Ph,C:NLi, from which unsolvated (Ph,C:NLi), may be obtained as a yellow amorphous and presumably polymeric solid, m. p. 260" (decomp.). Diphenylketiminoltthium forms the coloured crystalline adducts Ph,C:NLi,py, m. p. 108-1 10" (red)and Ph,C:NLi,tetrahydrofuran, m. p. 127" (orange) which dissociate in benzene and deposit (Ph,C:NLi),.Phenyl cyanide and methyl-lithium give yellow amorphous (PhCMe:NLi),t, m. p. 196". t-Butyl cyanide does not react with methyl-or ethyl-lithium a t or below 20". but methyl and ethyl cyanides with these alkyl-lithium compounds cleave alkane to give amorphous insoluble highly reactive solids believed to contain >C=C=N-groups. A similarly reactive and apparently polymeric, insoluble solid results when dimethylcyanamtde and methyl-lithium react and evolve methane. NNN'N'-Tetramethylguanidine and methyl-lithium give methane and the crystalline derivative [(Me,N),C:NLi],which is dimeric in benzene (by cryoscopy) and is also soluble in ether and toluene.DESPITE their frequent occurrence as intermediates in characterised. For example, although the derivatives reactions between elemental lithium or organolithium Ph,C:NLi and PhCMeINLi were recently used by Chan compounds and unsaturated nitrogen compounds or and Rochow 2 to prepare some azomethine derivatives compounds with N-H links, relatively few amino-of silicon, germanium, and tin, the lithium compounds derivatives of lithium, R2NLi, and no azomethine were not isolated. Such derivatives pose interesting derivatives, R2C:NLi, appear to have been isolated and structural and valence problems in that, if unsolvated, 1

Effect of ketimide ligand for ethylene polymerization and ethylene/norbornene copolymerization catalyzed by (cyclopentadienyl)(ketimide)titanium complexes–MAO catalyst systems: Structural analysis for Cp∗TiCl2(NCPh2)

“…Syntheses of Cp 0 TiCl 2 ½N@CðR 1 ÞR 2 ½Cp 0 ¼ Cp ð1Þ; C 5 Me 5 ðCp à ; 2Þ; R 1 ,R 2 = t Bu, t Bu (a), t Bu,Ph (b), Ph,Ph (c)], and structural analysis for Cp * TiCl 2 (N@CPh 2 ) Cp 0 TiCl 2 ðN@C t Bu 2 Þ ½Cp 0 ¼ Cp ð1aÞ; Cp à ð2aÞ were prepared by reaction of Cp 0 TiCl 3 with Li(N@C t Bu 2 ) in toluene according to the reported procedure [15a]. CpTiCl 2 [N@C ( t Bu)Ph] (1b), CpTiCl 2 (N@CPh 2 ) (1c), and Cp * TiCl 2 (N@CPh 2 ) (2c) were prepared similarly in moderate yields (69-93%) from Cp 0 TiCl 3 by treating with Li[N@C( t Bu)Ph] [22] or Li(N@CPh 2 ) [23] in toluene. The resultant complexes were identified by 1 H and 13 C NMR spectra and elemental analyses.…”

“…Syntheses of CpTiCl 2 (N@C t Bu 2 ) (1a), Cp * TiCl 2 (N @C t Bu 2 ) (2a) were according to the previous report [15a]. Li[N@C( t Bu)Ph] [22] or Li(N@CPh 2 ) [23] were prepared according to the reported procedures. Elemental analyses were performed by using PE2400II Series (Perkin-Elmer Co.), and some analysis runs were employed twice to confirm the reproducibility in the independent analysis/synthesis runs.…”

Iminoborylene complexes: evaluation of synthetic routes towards BN-allenylidenes and unexpected reactivity towards carbodiimides

“…20 Complex 3 was then treated with a series of ketiminolithium reagents LiNvCR 2 [R = t Bu/Ph/p-Tol/Mes/Trip (4a-e)], 21 to install the B-N linkage (Scheme 3, lower). 20 Complex 3 was then treated with a series of ketiminolithium reagents LiNvCR 2 [R = t Bu/Ph/p-Tol/Mes/Trip (4a-e)], 21 to install the B-N linkage (Scheme 3, lower).…”

Reactivity of Trivalent Ate Complex (thf)LiCe[N(SiHMe2)2]4 toward 1,1,3,3‐N,N,N′,N′‐Tetramethylguanidine

“…Guanidines are capable of stabilizing organometallic rare‐earth metal complexes in different ways . 1,1,3,3‐ N , N , N ′, N ′‐Tetramethylguanidine (HTMG) is such a multi‐functional compound applicable as a solvent for inorganic metal salts, as a neutral donor ligand, as a cationic complexation medium [H 2 TMG] + and, furthermore, as a monoanionic ligand [TMG] – . There are only a few lanthanide‐TMG derivatives reported in the literature, wherein TMG acts as an anionic ligand.…”