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The effect of coordination of alkanes, Xe and CO2 (η1-OCO) on changes in spin state and reactivity in organometallic chemistry: a combined experimental and theoretical study of the photochemistry of CpMn(CO)3.
Faraday Discussions ( IF 3.4 ) Pub Date : 2019-12-02 , DOI: 10.1039/c9fd00067d
Xue Wu 1 , Zhen Liu , Thomas S Murphy , Xue Z Sun , Magnus W D Hanson-Heine , Michael Towrie , Jeremy N Harvey , Michael W George
Affiliation  

A combined experimental and theoretical study is presented of several ligand addition reactions of the triplet fragment 3CpMn(CO)2 formed upon photolysis of CpMn(CO)3. Experimental data are provided for reactions in n-heptane and perfluoromethylcyclohexane (PFMCH), as well as in PFMCH doped with C2H6, Xe and CO2. In PFMCH we find that the conversion of 3CpMn(CO)2 to 1CpMn(CO)2(PFMCH) is much slower (τ = 18 (±3) ns) than the corresponding reactions in conventional alkanes (τ = 111 (±10) ps). We measure the effect of the coordination ability by doping PFMCH with alkane, Xe and CO2; these doped ligands form the corresponding singlet adducts with significantly variable formation rates. The reactivity as measured by the addition timescale follows the order 1CpMn(CO)2(C5H10) (τ = 270 (±10) ps) > 1CpMn(CO)2Xe (τ = 3.9 (±0.4) ns) ∼ 1CpMn(CO)2(CO2) (τ = 4.7 (±0.5) ns) > 1CpMn(CO)2(C7F14) (τ = 18 (±3) ns). Electronic structure theory calculations of the singlet and triplet potential energy surfaces and of their intersections, together with non-adiabatic statistical rate theory, reproduce the observed rates semi-quantitatively. It is shown that triplet adducts of the ligand and 3CpMn(CO)2 play a role in the kinetics, and account for the variable timescales observed experimentally.

中文翻译:

烷烃,Xe和CO2(η1-OCO)的配位对有机金属化学中自旋态和反应性变化的影响:CpMn(CO)3光化学的组合实验和理论研究。

结合实验和理论研究提出了对CpMn(CO)3进行光解后形成的三重态片段3CpMn(CO)2的几个配体加成反应。提供了在正庚烷和全氟甲基环己烷(PFMCH)中以及掺杂有C2H6,Xe和CO2的PFMCH中反应的实验数据。在PFMCH中,我们发现3CpMn(CO)2到1CpMn(CO)2(PFMCH)的转化要比常规烷烃中的相应反应(τ= 111(±10))慢得多(τ= 18(±3)ns) ps)。我们通过在PFMCH中掺入烷烃,Xe和CO2来测量配位能力的影响。这些掺杂的配体形成具有明显可变的形成速率的相应的单线态加合物。通过添加时标测量的反应性遵循以下顺序:1CpMn(CO)2(C5H10)(τ= 270(±10)ps)> 1CpMn(CO)2Xe(τ= 3.9(±0)。4)ns)〜1CpMn(CO)2(CO2)(τ= 4.7(±0.5)ns)> 1CpMn(CO)2(C7F14)(τ= 18(±3)ns)。单线态和三线态势能面及其相交的电子结构理论计算,与非绝热统计速率理论一起,以半定量方式再现了观察到的速率。结果表明,配体和3CpMn(CO)2的三重态加合物在动力学中起作用,并且说明了实验观察到的可变时标。
更新日期:2019-12-04
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