Transition Metal Complexes of Phosphinous Acids Featuring a Quasichelating Unit: Synthesis, Characterization, and Hetero-bimetallic Complexes

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• 作者：Nadine Allefeld ; Julia Bader ; Beate Neumann ; Hans-Georg Stammler ; Nikolai Ignat鈥檈v ; Berthold Hoge
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：August 17, 2015
• 年：2015
• 卷：54
• 期：16
• 页码：7945-7952
• 全文大小：475K
• ISSN：1520-510X

文摘

Diorganophosphane oxides were employed as preligands for the synthesis of catalytically active transition metal complexes of the phosphinous acids (CF₃)₂POH and (C₂F₅)₂POH. Their reactions with solid PtCl₂ and PdCl₂ led to the formation of mononuclear phosphinous acid complexes [Cl₂M{P(R^f)₂OH}₂] (M = Pd, Pt; R^f = C₂F₅, CF₃), which can be crystallized, for example, as its pyridinium salts, 2[HPy]⁺[Cl₂Pd{P(CF₃)₂O}₂]^{2鈥?/sup>. In vacuo HCl is liberated from the neutral palladium complexes affording mixtures of di- and polynuclear complexes. Moreover, (C₂F₅)₂POH was reacted with several 尾-diketonato complexes of palladium, platinum, and nickel yielding air- and moisture-stable complexes [(acac)M{[P(Rf)₂O]₂H}], featuring a quasichelating phosphinous acid phosphinito unit {P(Rf)₂O路路路H路路路O(Rf)₂P}鈭?/sup>. Treatment of [Ni(Cp)₂] (Cp = cyclopentadienyl) and [(cod)RhCl]₂ (cod = 1,5-cyclooctadiene) with (C₂F₅)₂POH leads to the substitution of one Cp or chloro ligand by a quasichelating unit. The novel coordination compounds were characterized by NMR and IR spectroscopies, mass spectrometry, and X-ray diffraction analysis. The platinum complex [(acac)Pt{[P(C₂F₅)₂O]₂H}] (acac = acetylacetonato) was used for the construction of hetero-bimetallic complexes by the treatment with [(cod)RhCl]₂ and [Ni(Cp)₂]. The trinuclear bimetallic complex [{(acac)Pt[P(C₂F₅)₂O]₂}₂Ni] is the first structurally characterized hetero-bimetallic species containing a bis(perfluoroalkyl)phosphinito bridge.}