Transition-Metal Complexes Containing Parent Phosphine or Phosphinyl Ligands and Their Use as Precursors for Phosphide Nanoparticles

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• 作者：Susanne Bauer ; Cornelia Hunger ; Michael Bodensteiner ; Wilfried-Solo Ojo ; Arnaud Cros-Gagneux ; Bruno Chaudret ; C茅line Nayral ; Fabien Delpech ; Manfred Scheer
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：November 3, 2014
• 年：2014
• 卷：53
• 期：21
• 页码：11438-11446
• 全文大小：432K
• ISSN：1520-510X

文摘

P鈥揌 functional transition-metal complexes were synthesized without using hazardous PH₃ gas in good yields by photolysis of the transition-metal carbonyl complexes M(CO)_6-x (M = Cr, W, Fe; x = 0, 1) in tetrahydrofuran followed by reaction with P₂(SiMe₃)₄ and subsequent methanolysis to give the bridging complexes [(CO)_xM(渭-PH₂)]₂ (M = Fe, x = 3 (1), M = Cr, x = 4 (2a), M = W, x = 4 (2b)). The photolysis of [(CO)₄M(渭-PH₂)]₂ (M = Cr (2a), M = W (2b)) with P(SiMe₃)₃ was applied followed by methanolysis to synthesize the PH₂ bridging transition-metal binuclear complexes with terminal PH₃ groups. The products [(CO)₄M(渭-PH₂)₂M(CO)₃(PH₃)] (M = Cr (3a), M = W (3b)) and [(CO)₄W(渭-PH₂)₂W(CO)₂(PH₃)₂] (4b) were isolated in moderate yield. Another synthetic approach to this type of compounds is the direct photolysis of the complexes [(CO)₃M(PH₃)₃] (M = Cr (5a), M = W (5b)). The products were comprehensively characterized by ³¹P NMR and IR spectroscopy as well as by X-ray structural analysis. Additionally, the relevancy of 2a as single source precursor for the synthesis of stoichiometry-controlled CrP nanoparticles has been demonstrated.