Vanessa R. G. Cacho, Luís F. Veiros, Clara S. B. Gomes, Mariana Sardo, Cláudia A. Figueira, Ana M. Martins and Maria João Ferreira*,
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引用次数: 0
摘要
考察了2-（二叔丁基磷酰）甲基吡啶L1和2-（二叔丁基磷酰）吡啶L2负载的氢化钌配合物的反应性。{Ru(COD)Cl2}x与L1在碱和10 bar H2存在下反应得到预期的配合物[Ru(L1)2(H)Cl], 1，而与L2反应得到由C-P键断裂引起的配合物[Ru(L2)(P(H)tBu2)(H)Cl], 2。我们能够确定，在反应条件下，生成的第一种物质是[Ru(L2)2(H)Cl], 3，该物质分解生成络合物2，并与[Ru(L2)2Cl2]， 4达到平衡。DFT得到的机理是碳的质子化反应为最高能量阶（38.9 kcal/mol），符合慢反应。初步研究表明配合物2在苯甲醛加氢反应中是一种非常活跃的催化剂（吨可达44,000吨）。
C–P Bond Cleavage Through Hydrogenation in Ruthenium Complexes Supported by P,N Ligands
The reactivity of ruthenium hydride complexes supported by 2-((di-tert-butylphosphaneyl)methyl)pyridine, L1 and 2-(di-tert-butylphosphaneyl)pyridine, L2, was explored. The reaction of {Ru(COD)Cl2}x with L1 in the presence of base and 10 bar of H2 gave the expected complex [Ru(L1)2(H)Cl], 1, while the same reaction with L2 gave [Ru(L2)(P(H)tBu2)(H)Cl], 2, that results from the cleavage of a C–P bond. We were able to establish that under the reaction conditions the first species formed is [Ru(L2)2(H)Cl], 3, and that this species decomposes to give complex 2 and is in equilibrium with [Ru(L2)2Cl2], 4. The proposed mechanism obtained by DFT has the protonation of the carbon as the highest energy step (38.9 kcal/mol), consistent with a slow reaction. Preliminary studies reveal that complex 2 is a very active catalyst in the hydrogenation of benzaldehyde (TONs up to 44,000).
期刊介绍：
Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.
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