SYNTHETIC, STRUCTURAL, SPECTROSCOPIC AND CALCULATIONAL STUDIES OF A LITHIUM BETA-DIKETINIMATE COMPLEX

Mair FS.; Edwards AJ.; Raithby PR.; Snaith R.; Scully D.

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SYNTHETIC, STRUCTURAL, SPECTROSCOPIC AND CALCULATIONAL STUDIES OF A LITHIUM BETA-DIKETINIMATE COMPLEX

机译：贝塔-二酮亚氨酸锂络合物的合成，结构，光谱和计算研究

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Reaction of malonaldehyde bis(phenylimine) monohydrochloride with two equivalents of n-BuLi in the presence of hexamethylphosphoric triamide (HMPA) yielded crystals of [PhN(CH)(3)NPhLi . HMPA](2). The two LiN2C3 metallacycles of the dimeric molecule are linked by two bridging oxygens from HMPA. No spectroscopic evidence for dissociative or other equilibria was obtained. The lithium projects above the mean plane of the metallacycles. MNDO calculations on model compounds reproduced bond lengths and angles well, except that all minima were planar, ascribing the envelope conformation to a packing effect. The molecule could best be described as a 1,5-diphenyl-1,5-diazapentadienyl lithium complex, the anion having contributions from diketinimato and two equivalent keteneimine-ene-amido resonance forms. In contrast, the protonated ligand exists in a localized keteneimine-ene-amine form only. [References: 16]

机译：丙二醛双（苯基亚胺）一盐酸盐与六当量的正丁基锂在六甲基磷酸三酰胺（HMPA）存在下反应，生成[PhN（CH）（3）NPhLi晶体。 HMPA]（2）。二聚体分子的两个LiN2C3金属环通过来自HMPA的两个桥接氧连接。没有解离或其他平衡的光谱证据。锂突出到金属环的平均平面之上。 MNDO对模型化合物的计算很好地再现了键的长度和角度，除了所有最小值均为平面之外，这归因于包封构象的堆积效应。该分子可以最好地描述为1,5-二苯基-1,5-二氮杂戊二烯基锂络合物，该阴离子具有双酮亚胺和两个等效的酮亚胺-烯-氨基共振形式的贡献。相反，质子化的配体仅以局部的烯酮亚胺-烯胺形式存在。 [参考：16]

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《Polyhedron: The International Journal for Inorganic and Organometallic Chemistry》 |1995年第18期|共5页
作者
Mair FS.; Edwards AJ.; Raithby PR.; Snaith R.; Scully D.;
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正文语种 eng
中图分类化学;无机化学;
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Crystal-structure;

机译：晶体结构;

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1. SYNTHETIC, STRUCTURAL, SPECTROSCOPIC AND CALCULATIONAL STUDIES OF A LITHIUM BETA-DIKETINIMATE COMPLEX [J] . Mair FS., Edwards AJ., Raithby PR., Polyhedron: The International Journal for Inorganic and Organometallic Chemistry . 1995,第17a18期

机译：贝塔-二酮亚氨酸锂络合物的合成，结构，光谱和计算研究
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SYNTHETIC, STRUCTURAL, SPECTROSCOPIC AND CALCULATIONAL STUDIES OF A LITHIUM BETA-DIKETINIMATE COMPLEX

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