Chemistry of [(1H-hydronaphthalene)Mn(CO)3]: The Role of Ring-Slippage in Substitution, Catalytic Hydrosilylation, and Molecular Crystal Structure of [(η3-C10H9)Mn(CO)3P(OMe)3]
Chemistry of [(1H-hydronaphthalene)Mn(CO)3]: The Role of Ring-Slippage in Substitution, Catalytic Hydrosilylation, and Molecular Crystal Structure of [(η3-C10H9)Mn(CO)3P(OMe)3]
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DOI：
10.1021/om9903386
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发表时间：
1999-09
期刊：
影响因子：
2.8
通讯作者：
S. U. Son;Se-Jung Paik;In Su Lee;Young-a Lee;Y. Chung;Won K. Seok;Heung-N. Lee
中科院分区：
文献类型：
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作者：
S. U. Son;Se-Jung Paik;In Su Lee;Young-a Lee;Y. Chung;Won K. Seok;Heung-N. Lee
[（η_5-C_10H_9）Mn（CO）_3]（1）与L反应，高产率地生成[（η_3-C_10H_9）Mn（CO）_3L]（2，L = P（OMe）_3; 5，L = CO）。2的X射线结构分析证实了1-氢化萘环的η3键模式。2的热处理得到[（η5-C10 H9）Mn（CO）2 P（OMe）3]（3）。1中的η5-1-氢化萘环非常容易开环，η5参与者3。1与P（OMe）3反应的动力学研究表明，2的生成在1中为一级反应，在P（OMe）3中为一级反应，活化参数如下：ΔH = 6.9 ± 0.4 kcal/mol; ΔS = −32.6 ± 1.5 eu。在130 °C下，茚基配合物[（η5-C9 H7）Mn（CO）3]与P（OEt）3和1与P（OMe）3的反应性的定量比较表明，1的反应速率常数比茚基配合物快2 × 106倍。1中的巨大速率增强被合理化为第二个苯环对2的稳定。并将其应用于[（η6-C10 H8）Mn（CO）2 P（OMe）3] BF_4的合成和催化加氢反应中。
Reaction of [(η5-C10H9)Mn(CO)3] (1) with L produced [(η3-C10H9)Mn(CO)3L] (2, L = P(OMe)3; 5, L = CO) in high yields. X-ray structural analysis of 2 confirmed an η3-bonding mode of the 1-hydronaphthalene ring. Thermal treatment of 2 led to [(η5-C10H9)Mn(CO)2P(OMe)3] (3). The η5-1-hydronaphthalene ring in 1 is quite easily ring-slipped, η5 ↔ η3. A kinetic study of the reaction of 1 with P(OMe)3 indicates that formation of 2 is first order in 1 and first order in P(OMe)3 with the following activation parameters: ΔH⧧ = 6.9 ± 0.4 kcal/mol; ΔS⧧ = −32.6 ± 1.5 eu. Quantitative comparison between the reactivity of the indenyl complex [(η5-C9H7)Mn(CO)3] with P(OEt)3 and 1 with P(OMe)3 at 130 °C shows that the rate constant for 1 is 2 × 106 times faster than that of the indenyl complex. The tremendous rate enhancement in 1 was rationalized as a stabilization of 2 by the second benzene ring. The facile ring-slippage in 1 has been utilized in the synthesis of [(η6-C10H8)Mn(CO)2P(OMe)3]BF4 and in the catalytic hydrosi...