Synthetic, structural, spectroscopic and calculational studies of a lithium β-diketinimate complex
作者： F.S. Mair , D. Scully , A.J. Edwards , P.R. Raithby , R. Snaith
DOI: 10.1016/0277-5387(95)00073-2
关键词: Protonation 、 MNDO 、 Ion 、 Chemistry 、 Stereochemistry 、 Molecule 、 Bond length 、 Crystallography 、 Hexamethylphosphoric Triamide
摘要: Abstract Reaction of malonaldehyde bis(phenylimine) monohydrochloride with two equivalents n-BuLi in the presence hexamethylphosphoric triamide (HMPA) yielded crystals [PhN(CH)3NPhLi·HMPA]2. The LiN2C3 metallacycles dimeric molecule are linked by bridging oxygens from HMPA. No spectroscopic evidence for dissociative or other equilibria was obtained. lithium projects above mean plane metallacycles. MNDO calculations on model compounds reproduced bond lengths and angles well, except that all minima were planar, ascribing envelope conformation to a packing effect. could best be described as 1,5-diphenyl-1,5-diazapentadienyl complex, anion having contributions diketinimato equivalent keteneimine-ene-amido resonance forms. In contrast, protonated ligand exists localized keteneimine-ene-amine form only.
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