Synthesis of Quinoline-Based Rh–Sb Complexes: Inhibition of Halide Transfer to Access a Rh→Sb Z-Type Interaction

IF 2.9 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2025-08-01 DOI:10.1021/acs.organomet.5c00187

Xinrui Ou, Fanji Kong, Kevin P. Quirion, Christopher K. Webber, Diane A. Dickie, Daniel H. Ess and T. Brent Gunnoe*,

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引用次数: 0

Abstract

We report the synthesis of Rh–Sb complexes using high valent Sb ligands, Q₃SbCl₂ (1, Q = 8-quinolinyl) and Q₃SbF₂ (2), from the low valent Rh precursor [(CO)₂Rh(μ-Cl)]₂ to afford the complexes [(κ⁴-Q₃SbCl)Rh(CO)Cl][(CO)₂RhCl₂] (3) and (κ⁴-Q₃SbF₂)Rh(CO)Cl (4), respectively. The reaction of 1 with [(CO)₂Rh(μ-Cl)]₂ results in the transfer of chloride from Sb to Rh to give the ion pair 3 with a Rh–Sb bond for the cation that, according to computational analysis, has some covalent character. Replacing Sb–Cl with Sb–F bonds (i.e., compound 2) inhibited halide transfer and allowed formation of 4 with a Rh→Sb interaction that has more Z-type character than the Rh–Sb bond for complex 3. Molecular orbital and localized orbital bonding analyses are consistent with the proposed Rh→Sb interaction of 4 being more Z-type in character.

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喹啉类Rh - Sb配合物的合成：抑制卤化物转移以获得Rh→Sb z型相互作用

本文报道了以低价Rh前体[(CO)2Rh(μ-Cl)]2为原料，用高价Sb配体Q3SbCl2 （1, Q = 8-喹啉基）和Q3SbF2(2)合成Rh - Sb配合物，分别得到配合物[(CO)2RhCl2](3)和（κ4-Q3SbF2）Rh(CO)Cl(4)]。1与[(CO)2Rh(μ-Cl)]2的反应导致氯离子从Sb转移到Rh，得到具有Rh - Sb键的离子对3，根据计算分析，阳离子具有一定的共价特征。用Sb - f键取代Sb - cl键（即化合物2）抑制了卤化物转移，并允许形成具有Rh→Sb相互作用的4，该相互作用比配合物3的Rh - Sb键更具z型特征。分子轨道和定域轨道成键分析与提出的4的Rh→Sb相互作用更具有z型特征相一致。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Organometallics 化学-无机化学与核化学

CiteScore

5.60

自引率

7.10%

发文量

382

审稿时长

1.7 months

期刊介绍： Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.