Phosphido complexes derived from 1,1'-ferrocenediyl-bridged secondary diphosphines.

Phosphido complexes derived from 1,1'-ferrocenediyl-bridged secondary diphosphines.
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衍生自 1,1-二茂铁二基桥联仲二膦的磷基复合物

DOI:
10.1039/c7dt00941k
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发表时间:
2017
影响因子:
4
通讯作者:
U. Siemeling
U. Siemeling
中科院分区:
化学2区
文献类型:
--
作者:
S. Hitzel;C. Färber;C. Bruhn;U. Siemeling

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本文主要研究了二茂铁基的[Fe{η5-C5 H4(PHR)}2]型仲二膦化合物,它们的P-取代基分别为甲基、新戊基(Np)、叔丁基、苯基和3,5-双(三氟甲基)苯基(XyF),具有明显不同的空间和电子性质。[Fe{η5-C5 H4(PHPh)}2](H21 a)和[Fe{η5-C5 H4(PHt-Bu)}2](H21 b)与n-BuLi在TMEDA存在下反应得到了含有环状非平面Li 2 P2核的[Li 2(μ-1)(TMEDA)2]型二磷化锂。[Fe{η5-C5 H4(PHMe)}2](H21 c)和[Fe{η5-C5 H4(PHNp)}2](H21 d)的类似反应提供了表现出梯形Li 4P 4基序的二聚体聚集体,即[Li 4(μ-1c 2(TMEDA)3]和[Li 2(μ-1d)(TMEDA)]2。H21 e(R = XyF)不能提供稳定的二磷化锂。Zr(NMe 2)4与芳基取代的化合物H21 a和H21 e可能发生Brønsted复分解反应,生成[{Zr(NMe 2)3}2(μ-1)]型产物。相反,烷基取代的同系物H21 b-H21 d对Zr(NMe 2)4是惰性的。[Fe{η_5-C_5H_4(PHR)}_2]与二茂镍的反应得到了H_21c和H_21e的许多产物的难处理的混合物。在另外三种情况下,分离出[(NiCp)2(μ-1)]型化合物。对于H21 b和H21 d,观察到通过[NiCp(H1)]类型的膦基-膦基中间体的两步反应,其可以在[NiCp(H1b)]的情况下分离和充分表征。
This paper focuses on ferrocene-based secondary diphosphines of the type [Fe{η5-C5H4(PHR)}2] with P-substituents of distinctly different steric and electronic properties, namely methyl, neopentyl (Np), tert-butyl, phenyl and 3,5-bis(trifluoromethyl)phenyl (XyF). The reaction of [Fe{η5-C5H4(PHPh)}2] (H21a) and [Fe{η5-C5H4(PHt-Bu)}2] (H21b) with n-BuLi in the presence of TMEDA afforded lithium diphosphides of the type [Li2(μ-1)(TMEDA)2], which contain a cyclic non-planar Li2P2 core. The analogous reactions of [Fe{η5-C5H4(PHMe)}2] (H21c) and [Fe{η5-C5H4(PHNp)}2] (H21d) furnished dimeric aggregates exhibiting a ladder-type Li4P4 motif, viz. [Li4(μ-1c)2(TMEDA)3] and [Li2(μ-1d)(TMEDA)]2. H21e (R = XyF) did not afford a stable lithium diphosphide. A Brønsted metathesis with Zr(NMe2)4 was possible with the aryl-substituted compounds H21a and H21e, leading to products of the type [{Zr(NMe2)3}2(μ-1)]. In contrast, the alkyl-substituted congeners H21b–H21d were inert towards Zr(NMe2)4. The reaction of [Fe{η5-C5H4(PHR)}2] with nickelocene afforded intractable mixtures of numerous products in the case of H21c and H21e. In the other three cases, compounds of the type [(NiCp)2(μ-1)] were isolated. For H21b and H21d a two-stepped reaction via a phosphino–phosphido intermediate of the type [NiCp(H1)] was observed, which could be isolated and fully characterised in the case of [NiCp(H1b)].
DOI: 10.1039/c39820000220
发表时间: 1982
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影响因子: --
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发表时间: 2001
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