C–P Bond Cleavage Through Hydrogenation in Ruthenium Complexes Supported by P,N Ligands

IF 4.3 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2024-11-26 DOI:10.1021/acs.inorgchem.4c04275

Vanessa R. G. Cacho, Luís F. Veiros, Clara S. B. Gomes, Mariana Sardo, Cláudia A. Figueira, Ana M. Martins, Maria João Ferreira

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Abstract

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).

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P,N 配体支持的钌配合物中通过氢化作用裂解 C-P 键

研究人员探索了 2-((二叔丁基膦烷基)甲基)吡啶（L1）和 2-(二叔丁基膦烷基)吡啶（L2）支持的氢化钌配合物的反应性。在碱和 10 bar H2 的存在下，{Ru(COD)Cl2}x 与 L1 反应生成预期的复合物 [Ru(L1)2(H)Cl]，即 1，而与 L2 反应生成 [Ru(L2)(P(H)tBu2)(H)Cl]，即 2，它是 C-P 键裂解的结果。我们能够确定，在反应条件下形成的第一个物种是[Ru(L2)2(H)Cl]，3，该物种分解后得到复合物 2，并与[Ru(L2)2Cl2]，4 处于平衡状态。根据 DFT 得出的拟议机理，碳的质子化是能量最高的步骤（38.9 kcal/mol），与缓慢反应一致。初步研究表明，配合物 2 在苯甲醛氢化过程中是一种非常活跃的催化剂（吨当量高达 44,000）。

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

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.