非对称膦吡啶-1,8-萘啶 PNNN 配体的钌、铜和钌铜配合物

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions Pub Date : 2024-10-15 DOI:10.1039/D4DT02755H

Jingyun Wu, Michael A. Stevens, Michael G. Gardiner and Annie L. Colebatch

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引用次数: 0

摘要

报告了一种新的非对称二核膦基吡啶-1,8-萘啶配体 PNNN。与 CuCl 反应生成了二铜络合物 [Cu2(µ-Cl)2(PNN)]（1）。与此相反，[RuCl2(cymene)]2 的络合产生了单金属物种 [RuCl(cymene)(PNNN)]Cl（[2]Cl），其中的 Ru 与 κ2-N,N 结合，而不是与 κ2-P,N 结合。单钌络合物 [2]Cl 的选择性形成使得[RuCuCl3(cymene)(PNNN)]（3）和[RuCuCl2(cymene)(PNNN)]2[PF6]2（[4]2[PF6]2）这两种杂多金属络合物得以合成，它们都表现出 Cu 的κ1-P 配位。配合物 1 和 [4]2[PF6]2 依次经碱（KOtBu）和酸（HCl）处理后，在金属配体合作亚甲基位点上表现出可逆的脱芳基化-芳基化行为。值得注意的是，[4]2[PF6]2 的去质子化会导致铜的配位模式转变为 κ2-P,N。

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Ruthenium, copper and ruthenium–copper complexes of an unsymmetrical phosphino pyridyl 1,8-naphthyridine PNNN ligand†

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Ruthenium, copper and ruthenium–copper complexes of an unsymmetrical phosphino pyridyl 1,8-naphthyridine PNNN ligand†

A new unsymmetrical dinucleating phosphino pyridyl 1,8-naphthyridine ligand PNNN is reported. Reaction with CuCl gave the dicopper complex [Cu₂(μ-Cl)₂(PNNN)] (1). In contrast, complexation of [RuCl₂(cymene)]₂ yielded a monometallic species [RuCl(cymene)(PNNN)]Cl ([2]Cl) in which the Ru is bound to the κ²-N,N, rather than κ²-P,N, binding pocket. The selective formation of the monoruthenium complex [2]Cl enabled synthesis of heterobimetallic complexes [RuCuCl₃(cymene)(PNNN)] (3) and [RuCuCl₂(cymene)(PNNN)]₂[PF₆]₂ ([4]₂[PF₆]₂), which both exhibit κ¹-P coordination of Cu. Complexes 1 and [4]₂[PF₆]₂ exhibit reversible dearomatisation–aromatisation behaviour at the metal–ligand cooperative methylene site upon sequential treatment with base (KO^tBu) and acid (HCl). Notably, deprotonation of [4]₂[PF₆]₂ induces a shift in the coordination mode of Cu to κ²-P,N.

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来源期刊

Dalton Transactions 化学-无机化学与核化学

CiteScore

6.60

自引率

7.50%

发文量

1832

审稿时长

1.5 months

期刊介绍： Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.