Structure and Lewis-base reactivity of bicyclic low-valent germanium and tin complexes bridged by bis(diisopropylphosphino)amine

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• 作者：Christopher J. Miller^a ; Ujwal Chadha^a ; Jordan R. Ulibarri-Sanchez^a ; Diane A. Dickie^a ; Richard A. Kemp^a ; ^b ; ^{rakemp@unm.edu" class="auth_mail" title="E-mail the corresponding author}
• 关键词：Group 14 elements ; Phosphine ligands ; X-ray crystallography ; Multinuclear NMR ; Small molecule activation
• 刊名：Polyhedron
• 出版年：2016
• 出版时间：16 August 2016
• 年：2016
• 卷：114
• 期：Complete
• 页码：351-359
• 全文大小：1490 K

文摘

Lithium bis(diisopropylphosphino)amide LiN[P(i-Pr)₂]₂ reacts with SnCl₂ or GeCl₂·dioxane in the presence of excess n-BuLi to produce the bicyclic compounds {MN[P(i-Pr)₂]₂}₂ (M = Sn, Ge) which feature Sn₂²⁺ or Ge₂²⁺ units bridged by phosphorus. When paired with B(C₆F₅)₃ in THF, the Lewis-basic M₂²⁺ complexes participate in a THF ring-opening reaction. Quite surprisingly, in the absence of THF one para-F atom from B(C₆F₅)₃ is activated and displaced to B while a new M–C bond is formed. Each of these complexes, as well as Cl₂Sn{N[P(i-Pr)₂]₂}₂ and {ClSnN[P(i-Pr)₂]₂}₂ were characterized by a combination of multi-nuclear NMR spectroscopy and single-crystal X-ray diffraction.