Geminal arsa(III)amide and trisubstituted antimony and bismuth amides from the sterically hindered, N-functionalised amido ligand [{2-(6-Me)C5H3N}NSiMe3]−
Geminal arsa(III)amide and trisubstituted antimony and bismuth amides from the sterically hindered, N-functionalised amido ligand [{2-(6-Me)C5H3N}NSiMe3]−
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来自空间位阻、N-功能化酰胺配体 [{2-(6-Me)C5H3N}NSiMe3]− 的孪生 arsa(III) 酰胺和三取代锑和铋酰胺
DOI：
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发表时间：
2000
期刊：
影响因子：
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通讯作者：
Allan H. White
中科院分区：
文献类型：
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作者：
C. Raston;B. Skelton;Vicki;Allan H. White
二聚二乙醚溶剂化的氨基锂，双[{2-(6-甲基)吡啶基}三甲基甲硅烷基氨基锂二醚]与二当量的三氯化砷(III)在乙醚中反应，得到氨基二氯化砷化合物[{2-(6-Me)C5H3N}NSiMe3(AsCl2)](1)，而四当量的砷(III)三氯化物在乙醚中通过 N-Si 键断裂得到络合物 [{2-(6-Me)C5H3N}N(AsCl2)2] (3)。该化合物也是从之前报道的化合物 [{2-(6-Me)C5H3N}NAsCl]2 (2) 与两当量 AsCl3 在甲苯中的再分布反应中分离出来的。 (3)的晶体结构表明它是具有两个偕AsCl2基团的单体。一个砷中心具有金字塔几何形状，另一个四坐标砷中心具有扭曲的三角双锥几何形状，假定的孤对电子占据赤道位置。由MCl3 (M = Sb, Bi) 和二聚氨基锂按2:3 化学计量反应制备均配三酰胺-锑和-铋配合物。酰胺氮中心与金属中心配位，每个配体螯合金属，使其具有六重配位。 M-N（酰胺）键比 M-N（吡啶基）键短得多，这表明假定孤对电子与 [N(pyr)]3 平面相交。这使得分子具有扭曲的八面体形状和非晶体 C3 轴。
The reaction of the dimeric diethyl ether solvated lithium amide, bis[{2-(6-methyl)pyridyl}trimethylsilylamidolithium dietherate], with two equivalents of arsenic(III) trichloride in diethyl ether affords the amido arsenic dichloride compound [{2-(6-Me)C5H3N}NSiMe3(AsCl2)] (1), while four equivalents of arsenic(III) trichloride in diethyl ether gives the complex [{2-(6-Me)C5H3N}N(AsCl2)2] (3) through the cleavage of the N–Si bond. This compound is also isolated from the redistribution reaction of the previously reported compound [{2-(6-Me)C5H3N}NAsCl]2 (2) with two equivalents of AsCl3 in toluene. The crystal structure of (3) shows it to be monomeric with two geminal AsCl2 groups. One arsenic centre has pyramidal geometry with the other four-coordinate arsenic centre having distorted trigonal bipyramidal geometry with the putative lone pair of electrons occupying an equatorial position. Homoleptic triamido–antimony and –bismuth complexes are prepared from the 2∶3 stoichiometric reaction of MCl3 (M = Sb, Bi) and dimeric lithium amide. The amide nitrogen centres are coordinated fac to the metal centre with each ligand chelating the metal giving it six-fold coordination. The M–N(amide) bonds are much shorter than the M–N(pyridyl) bonds, suggestive of a putative lone pair of electrons intersecting the [N(pyr)]3 plane. This gives the molecule a distorted octahedral shape with a non-crystallographic C3 axis.