Roles of a tetrahydroborate ligand in a facile route to ruthenium(II)ethyl hydride complexes,and a kinetic study of ethane reductive elimination

Simon B.Duckett; J.Claire Loiwe; John P.Lowe; Roge rJ.Mawby

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Roles of a tetrahydroborate ligand in a facile route to ruthenium(II)ethyl hydride complexes,and a kinetic study of ethane reductive elimination

机译：四氢硼酸酯配体在钌（II）氢化物络合物的简便合成中的作用以及乙烷还原消除的动力学研究

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The tetrahydroborate ligand in[Ru(eta~2-BH_4)(CO)H(PME_2Ph)_2],1,allows conversion under very mild conditions to[Ru(CO)(Et)H(PME_2Ph)_3],7,by way of[Ru(eta~2-BH_4)(CO)Et(PME_2Ph)_2],4.Deprotection of the hydride ligand in 7(by BH_3 abstraction)occurs only in the final step,thus preventing premature ethane elimination.A deviation from the route from 4 to 7 yields[Ru(eta~2-BH_4)(COEt)(PME_2Ph)_3],6,but does not prevent ultimate conversion to 7.Modification of the treatment of 4 yields an isomer of 7,10.Both isomers eliminate ethane at temperatures above 250 K:the immediate product of elimination,thought to be[Ru(CO)(PME_2Ph)_3],11,can be trapped as[Ru(CO)(PME_2Ph)_4],12,[Ru(CO)H_2(PME_2Ph)_3],3a,or[Ru(CO)(C=CCMe_3)H(PME_2Ph)_3],13.The elimination is a simple first-order process with negative AS1* and(for 7)a normal kinetic isotope effect(k_H/k_D = 2.5 at 287.9 K).These results,coupled with labelling studies,rule out a rapid equilibrium with a delta-ethane intermediate prior to ethane loss.

机译：[Ru（eta〜2-BH_4）（CO）H（PME_2Ph）_2]，1中的四氢硼酸酯配体允许在非常温和的条件下通过以下方式转化为[Ru（CO）（Et）H（PME_2Ph）_3]，7 [Ru（eta〜2-BH_4）（CO）Et（PME_2Ph）_2]的方法，4。7中的氢化物配体脱保护（通过BH_3提取）仅在最后一步发生，从而防止了乙烷的过早消除。从4到7的路线生成[Ru（eta〜2-BH_4）（COEt）（PME_2Ph）_3]，6，但不会阻止最终转化为7。对4的处理进行修饰可以得到7,10的异构体两种异构体在高于250 K的温度下都能消除乙烷：消除的直接产物原本是[Ru（CO）（PME_2Ph）_3]，11，可能被捕集为[Ru（CO）（PME_2Ph）_4]，12， [Ru（CO）H_2（PME_2Ph）_3]，3a或[Ru（CO）（C = CCMe_3）H（PME_2Ph）_3]，13。消除是一个简单的一阶过程，其AS1 *为负且（对于7）正常的动力学同位素效应（在287.9 K时k_H / k_D = 2.5）。这些结果，加上标记研究，排除了乙烷损失前与δ-乙烷中间体的快速平衡s。

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《Dalton transactions: An international journal of inorganic chemistry》 |2004年第21期|共10页
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Simon B.Duckett; J.Claire Loiwe; John P.Lowe; Roge rJ.Mawby;
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1. Roles of a tetrahydroborate ligand in a facile route to ruthenium(II)ethyl hydride complexes,and a kinetic study of ethane reductive elimination [J] . Simon B.Duckett, J.Claire Loiwe, John P.Lowe, Dalton transactions: An international journal of inorganic chemistry . 2004,第21期

机译：四氢硼酸酯配体在钌（II）氢化物络合物的简便合成中的作用以及乙烷还原消除的动力学研究
2. Use of the tetrahydroborate ligand as "gate-keeper" and protected hydride ligand: preparation and study of alkyl hydride and acyl hydride complexes of ruthenium(II) [J] . Duckett SB, Lowe JP, Mawby RJ Dalton transactions: An international journal of inorganic chemistry . 2006,第22期

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Roles of a tetrahydroborate ligand in a facile route to ruthenium(II)ethyl hydride complexes,and a kinetic study of ethane reductive elimination

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