Transition-metal complexes containing parent phosphine or phosphinyl ligands and their use as precursors for phosphide nanoparticles.
Transition-metal complexes containing parent phosphine or phosphinyl ligands and their use as precursors for phosphide nanoparticles.
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DOI：
10.1021/ic5012082
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发表时间：
2014-10
影响因子：
4.6
通讯作者：
Susanne Bauer;Cornelia Hunger;M. Bodensteiner;Wilfried-Solo Ojo;Arnaud Cros-Gagneux;B. Chaudret;C. Nayral;F. Delpech;M. Scheer
中科院分区：
文献类型：
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作者：
Susanne Bauer;Cornelia Hunger;M. Bodensteiner;Wilfried-Solo Ojo;Arnaud Cros-Gagneux;B. Chaudret;C. Nayral;F. Delpech;M. Scheer
过渡金属羰基配合物M(CO)(6-x)(M=Cr，W，Fe；x=0，1)在四氢呋喃中光解，然后与P2(SiMe3)4反应，再经醇解得到桥联配合物[(CO)(X)M(μ-Ph_2)]2(M=Fe，x=3(1)，M=Cr，x=4(2a)，M=W，x=4(2b))。将[(CO)4M(μ-Ph_2)]_2(M=Cr(2a)，M=W(2b))与P(SiMe_3)_3光解，再经甲醇分解，合成了端基为Ph_3的桥联过渡金属双核配合物。产物[(CO)4M(μ-Ph_2)2M(CO)_3(Ph_3)](M=Cr(3a)，M=W(3b))和[(CO)_4W(μ-Ph_2)2W(CO)_2(Ph_3)_2](4b)。另一种合成这类化合物的方法是直接光解[(CO)3M(Ph_3)_3](M=Cr(5a)，M=W(5b))。产物用~(31)P核磁共振、红外光谱和X-射线结构分析进行了综合表征。此外，还证明了2a作为化学计量比控制的CRP纳米颗粒合成的单一来源前体的相关性。
P-H 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)(x)M(μ-PH2)]2 (M = Fe, x = 3 (1), M = Cr, x = 4 (2a), M = W, x = 4 (2b)). The photolysis of [(CO)4M(μ-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(μ-PH2)2M(CO)3(PH3)] (M = Cr (3a), M = W (3b)) and [(CO)4W(μ-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 (31)P 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.