A late-transition metal oxo complex: K7Na9[O=PtIV(H2O)L2]. L = [PW9O34]9- (Retracted Article)
A late-transition metal oxo complex: K7Na9[O=PtIV(H2O)L2]. L = [PW9O34]9- (Retracted Article)
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DOI：
10.1126/science.1104696
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发表时间：
2004-12-17
期刊：
影响因子：
56.9
通讯作者：
Hill, CL
中科院分区：
文献类型：
--
作者：
Anderson, TM;Neiwert, WA;Hill, CL
后过渡金属元素的末端单氧代配合物长期以来被认为太不稳定而不能合成，因为氧电子和大多数拟合的金属d轨道之间的排斥。本文报道了一种侧接两个多钨酸盐配体K_7Na_9 [O=Pt（H_2O）L ~（-2）]，L = [PW_9O_（34）]（9 ~-）的铂（Ⅳ）氧代化合物，在室温下为棕色晶体。在30开尔文的X射线和中子衍射显示了一个非常短的[1.720（18）埃] Pt-O键，没有证据表明在末端氧处有氢原子，排除了更好的Pt-OH络合物。密度泛函理论和光谱数据占的Pt（IV）-氧代单元的电子撤回到离域轨道的聚钨酸盐的稳定性。
Terminal mono-oxo complexes of the late transition metal elements have long been considered too unstable to synthesize because of repulsion between the oxygen electrons and the mostly fitted metal d orbitals. A platinum(IV)-oxo compound flanked by two polytungstate ligands, K7Na9[O=Pt(H2O)L-2], L = [PW9O34](9-), has now been prepared and isolated at room temperature as air-stable brown crystals. X-ray and neutron diffraction at 30 kelvin revealed a very short [1.720(18) angstrom] Pt-O bond and no evidence of a hydrogen atom at the terminal oxygen, ruling out a better precedented Pt-OH complex. Density functional theory and spectroscopic data account for the stability of the Pt(IV)-oxo unit by electron withdrawal into delocalized orbitals of the polytungstates.