The addition of oxygen to a Pt3Re cluster complex: a model for dissociative chemisorption of oxygen
The addition of oxygen to a Pt3Re cluster complex: a model for dissociative chemisorption of oxygen
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将氧添加到 Pt3Re 簇络合物中：氧解离化学吸附的模型
DOI：
10.1021/ja00070a046
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发表时间：
1993
影响因子：
15
通讯作者：
K. Muir
中科院分区：
文献类型：
--
作者：
Jianliang Xiao;J. Vittal;R. Puddephatt;L. Manojlović;K. Muir
本文报道了第一个将分子氧氧化加成到过渡金属簇中以得到双(t3-oxo)簇的例子。值得注意的是，该反应导致团簇的 4 电子氧化和 8 电子团簇电子数的增加，并且它为金属表面氧的解离化学吸附提供了一个简单的模型。这项工作显着增加了有机金属氧簇作为无机氧化物和表面结合氧化物的结构模型的已知价值，以及最近关于氧解离加成到多键二铼络合物的研究。1·2 配位不饱和簇阳离子 [ 3(μ3-€0)(μdppmjs]2"1" (1)，dppm = PhaPCLLPPha，已被证明是几种小分子化学吸附的良好模型。 Pt(l 11) 表面上的分子，3 但它无法与 Oz 反应。由于双金属 Pt-Re 催化剂可能比单独的铂更有用，因此有兴趣制备配位不饱和铂铼簇作为 Pt/Re 表面反应性的模型。 1 与 [Re(CO)s]- 产生新的簇阳离子 [Pts(Re(CO)3}^-dppm)3]+ (2).4簇 2 是带有 PFe~ 或 BPhr 阴离子的红黑晶体，2 的结构如图 1,4 所示。簇核心具有四面体几何形状，金属-金属键短且可能很强（表 I）。簇阳离子 2 的价电子数仅为 54，因此是配位不饱和的。5 对 2 中键合的最简单解释是三个填充键。 Pt3^-dppm)3 片段的 M-M 键合轨道（ai + e 对称性）充当 a 的三个空受体轨道（也是 ai + e 对称性）的供体
This article reports the first example of the oxidative addition of dioxygen to a transition-metal cluster to give a bis(/t3-oxo) cluster. Remarkably, this reaction leads to 4-electron oxidation of the cluster and an increase in the cluster electron count of 8-electrons, and it provides a simple model for the dissociative chemisorption of oxygen at a metal surface. This work adds significantly to the known value of organometallic oxo clusters as structural models for inorganic oxides and surface-bound oxide and to recent research on the dissociative addition of oxygen to multiply bonded dirhenium complexes.1·2 The coordinatively unsaturated cluster cation [ 3(μ3-€0)(μdppmjs]2"1" (1), dppm = PhaPCLLPPha, has been shown to be a good model for chemisorption of several small molecules at a Pt(l 11) surface,3 but it fails to react with Oz. Since bimetallic Pt-Re catalysts may be more useful than platinum alone, it was of interest to prepare coordinatively unsaturated platinumrhenium clusters as models for reactivity at the Pt/Re surface. Reaction of 1 with [Re(CO)s]-gave the new cluster cation [Pts(Re(CO)3}^-dppm)3]+ (2).4 The cluster 2 was obtained as redblack crystals with either PFe~ or BPhr anions, and the structure of 2 as the [BPI14] salt is shown in Figure 1,4 The cluster core has tetrahedral geometry, and the metal-metal bonds are short and presumably strong (Table I). The cluster cation 2 has a valence electron count of only 54 and so is coordinatively unsaturated.5 The simplest interpretation of the bonding in 2 is that the three filled M-M bonding orbitals (ai + e symmetry) of a Pt3^-dppm)3 fragment act as donors to the three vacant acceptor orbitals (also ai + e symmetry) of a