η3-Allyl Coordination at Pb(II)

η3-Allyl Coordination at Pb(II)
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Pb(II) 处的 η3-烯丙基配位

DOI:
10.1021/acs.organomet.8b00766
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发表时间:
2019
期刊:
影响因子:
2.8
通讯作者:
L. Wesemann
L. Wesemann
中科院分区:
化学2区
文献类型:
--
作者:
Sebastian Weiss;Maximilian Auer;K. Eichele;H. Schubert;L. Wesemann

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烯丙基氯化镁和甲基丙烯基溴化镁分别与大体积取代有机铅和有机锡卤化物(Ar*PbBr)2,(Ar′ PbBr)2,(Ar*SnCl)2(Ar* = 2,6-trip 2C 6 H3-,trip = 2,4,6-三异丙基苯基,Ar′ = 2,6-mes 2C 6 H3-,mes = 2,4,6-三甲基苯基)反应。烯丙基配体以η3-配位模式在有机亚丙基片段处配位。用晶体结构分析和Saunders同位素微扰技术表征了固体和溶液中的η3配位。对于亚铅Ar*Pb(C3 H5),可以获得固态207 Pb魔角旋转(MAS)NMR谱。各向同性的化学位移为−435 ppm,而207 Pb的化学位移张量为7000(500)ppm,是实验上观测到的最大值之一。甲基烯丙基配体在一个plumbylene片段协调表现出两个短和一个长的Pb-C相互作用。在与苯胺的反应中,烯丙基配体作为离去基团反应得到酰胺基亚铅基。
Allylmagnesium chloride and methyl-propenyl-magnesium bromide were reacted with bulky substituted organolead and organotin halides (Ar*PbBr)2, (Ar′PbBr)2, (Ar*SnCl)2 (Ar* = 2,6-trip2C6H3-, trip = 2,4,6-triisopropylphenyl, Ar′ = 2,6-mes2C6H3-, mes = 2,4,6-trimethylphenyl). The allyl ligand coordinates in an η3-coordination mode at organoplumbylene fragments. In the solid state as well as in solution, η3-coordination was characterized by crystal structure analysis and Saunders’ isotopic perturbation technique. For the plumbylene Ar*Pb(C3H5), a solid state 207Pb magic angle spinning (MAS) NMR spectrum could be obtained. The isotropic chemical shift is −435 ppm, and the magnitude of the 207Pb chemical shift tensor of 7000(500) ppm is among the greatest observed experimentally. The methylallyl ligand coordinated at a plumbylene fragment exhibits two short and one long Pb–C interaction. In reaction with aniline, the allyl ligand reacts as a leaving group to give amidoplumbylenes.
Ύ·(3)-锡(II)上的烯丙基配位-对炔烃和苯甲腈的反应性
DOI: 10.1002/anie.201500386
发表时间: 2015
期刊: Angewandte Chemie
影响因子: --
作者:
K. Krebs;J. Wiederkehr;J. Schneider;K. Eichele;H. Schubert;L. Wesemann
通讯作者: L. Wesemann