Synthesis and characterization of new triangulo derivatives of PtIPtIPtII, including the first platinum cluster binding both ethylene and CO
Synthesis and characterization of new triangulo derivatives of PtIPtIPtII, including the first platinum cluster binding both ethylene and CO
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PtIPtIPtII 的新型三角衍生物的合成和表征，包括第一个同时结合乙烯和 CO 的铂簇
DOI：
10.1021/om020027m
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发表时间：
2002
期刊：
影响因子：
2.8
通讯作者：
A. Albinati
中科院分区：
文献类型：
--
作者：
P. Leoni;F. Marchetti;M. Pasquali;Lorella Marchetti;A. Albinati
PtIPtIPtII三角簇Pt3(μ-PBut2)3(H)(CO)2(1)中的末端氢化物可以被单电子氧化剂（如[Cp2Fe]PF6）去除。在一氧化碳下，反应生成对称的阳离子衍生物[Pt3(μ-PBut2)3(CO)3]PF6(2)。通过过量的配体处理，我们还制备了[Pt3(μ-PBut2)3(CO)2(NCCH3)]PF6(3)和[Pt3(μ-PBut2)3(CO)2(CH2CH2)]PF6(4)。用异氰酸酯取代1中的CO配体，得到了新的中性三角形前体。用该方法分离得到了氢化物Pt3(μ-PBut2)3(H)(CNR)2 （5, R = CH2Ph; 6, R = C6H4-p-CH3; 7, R = But）。配合物7与氯仿反应生成Pt3(μ-PBut2)3(Cl)(CNBut)2(8)，当CNBut过量时，生成阳离子衍生物[Pt3(μ-PBut2)3(CNBut)3]Cl(9)。新的三角团簇通过多核磁共振谱和单晶x射线衍射进行了表征。
The terminal hydride in the PtIPtIPtII triangulo cluster Pt3(μ-PBut2)3(H)(CO)2 (1) may be removed by one-electron oxidants such as [Cp2Fe]PF6. Under carbon monoxide the reaction affords the symmetrical, cationic derivative [Pt3(μ-PBut2)3(CO)3]PF6 (2). By operating with an excess of the suitable ligand, we also prepared [Pt3(μ-PBut2)3(CO)2(NCCH3)]PF6 (3) and [Pt3(μ-PBut2)3(CO)2(CH2CH2)]PF6 (4). New neutral triangular precursors were obtained by substitution of the CO ligands contained in 1 with isocyanides. The hydrides Pt3(μ-PBut2)3(H)(CNR)2 (5, R = CH2Ph; 6, R = C6H4-p-CH3; 7, R = But) were isolated by this route. Complex 7 reacts with chloroform to give Pt3(μ-PBut2)3(Cl)(CNBut)2 (8), which, under an excess of CNBut, yields the cationic derivative [Pt3(μ-PBut2)3(CNBut)3]Cl (9). The new triangulo clusters were characterized by multinuclear NMR spectroscopy and, as far as 4 and 7 are concerned, by single-crystal X-ray diffraction.