Groups 9 and 10 Complexes of C–Donor Ligands Derived from Pyridinium-Stabilized Phosphorus Ylides

IF 2.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Organometallics Pub Date : 2024-07-04 DOI:10.1021/acs.organomet.4c00204

Anushree Poddar, F. Christopher Pigge

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Abstract

The design and synthesis of η¹-C-donor ligands that combine nucleophilic 4-alkylidene dihydropyridines with phosphorus ylides is reported. Positioning of a phosphonium group at the picolyl carbon of 4-alkylpyridinium salts allows for conversion to phosphonium-stabilized alkylidene dihydropyridine ligands under mildly basic conditions. The resulting (Me-N-Py-CH-PPh₂-R)(BF₄) ligands coordinate Pd(II)Cl₂ as monodentate (R = Ph) or bidentate ligands (R = 2-Py, CH₂PPh₂, or CH₂CH₂PPh₂), and six new Pd(II) complexes were spectroscopically characterized. Structural features of four of the complexes were further defined through single-crystal X-ray diffractometry. The ligands in these complexes are best described as phosphorus ylide C-donors that are stabilized by adjacent N-methylpyridinium rings. In addition, two Rh(I) complexes were successfully prepared and characterized, including a Rh(I) carbonyl complex which exhibited a low ν_CO of 1984 cm^–1, indicative of the strong σ-donor properties of these ligands. The ability of a Pd complex to catalyze Suzuki cross-coupling reactions was examined.

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由吡啶稳定磷酰化物衍生的第 9 和第 10 组 C 供体配体

报告设计并合成了将亲核的 4-亚烷基二氢吡啶与酰化磷结合在一起的 η1-C 供体配体。将鏻基团置于 4-烷基吡啶鎓盐的吡啶碳上，可在弱碱性条件下转化为鏻稳定的亚烷基二氢吡啶配体。由此得到的 (Me-N-Py-CH-PPh2-R)(BF4) 配体以单齿（R = Ph）或双齿配体（R = 2-Py、CH2PPh2 或 CH2CH2PPh2）的形式配位 Pd(II)Cl2，并对六种新的 Pd(II) 复合物进行了光谱表征。通过单晶 X 射线衍射仪进一步确定了其中四个配合物的结构特征。这些配合物中的配体被最好地描述为由相邻的 N-甲基吡啶鎓环稳定的磷矢量 C 供体。此外，还成功制备并表征了两种 Rh（I）配合物，其中一种 Rh（I）羰基配合物的 νCO 低至 1984 cm-1，表明这些配体具有很强的 σ-供体特性。研究还考察了钯配合物催化铃木交叉偶联反应的能力。

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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.