Characterization, Orbital Description, and Reactivity Patterns of Transition-Metal Oxo Species in the Gas Phase
Characterization, Orbital Description, and Reactivity Patterns of Transition-Metal Oxo Species in the Gas Phase
复制标题
气相过渡金属氧物种的表征、轨道描述和反应模式
DOI：
10.1007/3-540-46592-8_4
复制
发表时间：
2000
期刊：
影响因子：
56.9
通讯作者：
S. Shaik
中科院分区：
文献类型：
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作者：
D. Schröder;H. Schwarz;S. Shaik
金属氧基和过氧基物种在过渡金属催化氧化反应中起着关键作用，这一贡献涉及双原子金属氧基物种及其性质的气相研究，这对于理解观察到的反应模式是非常重要的。第二个话题涉及较高级的过渡金属氧化物，如二氧化物和三氧化物。对于这些物种，与相应的氧配合物存在结构上的二分性，例如，Mo_2、⇆、M(O2)。所描述的大多数基于金属的氧化都将不同自旋的表面之间的交叉作为关键步骤，并提出了破坏自旋守恒来确定晚期过渡金属氧化物的反应性。过渡金属通过自旋-轨道耦合来调节表面交叉的能力被介绍为氧化催化中的一个关键方面，但尚未被充分认识。进一步概述了这些基本性质如何与金属氧催化剂在凝聚相中的性质有关。
Metal-oxo and -peroxo species play key roles in catalytic oxidations using transition metals This contribution addresses gas-phase studies of diatomic metal-oxo species and their properties which turn out to be of prime importance for the understanding of the observed reactivity patterns. A second topic concerns higher transition-metal oxides such as di- and trioxides. For these species there exists a structural dichotomy with the corresponding dioxygen complexes, e.g., MO2 ⇆ M(O2). Most of the metal-based oxidations described involve crossings between surfaces of different spin as crucial steps, and the violation of spin conservation is proposed to determine the reactivity of the late transition-metal oxides. The ability of transition metals to mediate surface crossings via spin-orbit coupling is introduced as a key aspect in oxidation catalysis which has as yet not been fully appreciated. It is further outlined how these fundamental properties may relate to the properties of metal-oxo catalysts in the condensed phase.
DOI：
--
发表时间：
1996
期刊：
--
影响因子：
--
作者：
L. B. Knight;R. Babb;M. Ray;T. J. Banisaukas
通讯作者：
L. B. Knight;R. Babb;M. Ray;T. J. Banisaukas