Synthesis of a Stable Tricobalt Carbide Cluster

IF 14.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of the American Chemical Society Pub Date : 2025-05-29 DOI:10.1021/jacs.5c04760

Nicholas P. Litak, Shao-Liang Zheng, Dongtao Cui, Theodore A. Betley

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Abstract

We report the synthesis and characterization of the anionic tricobalt carbide cluster [(^FtbsL)Co₃(μ³–C)]⁻. The source of the carbide ligand is a phosphorus ylide (R₂MePCH₂; R = Me, Ph) which substitutes pyridine in the all-cobalt(II) cluster (^FtbsL)Co₃(py) to afford the ylide adduct (^FtbsL)Co₃(CH₂PMeR₂). Deprotonation affords the anionic diylide cluster [(^FtbsL)Co₃(κ²-η¹:η¹–(CH₂)₂PR₂)]⁻ which eliminates MePR₂ upon heating to furnish the anionic methylidyne cluster [(^FtbsL)Co₃(μ³–CH)]⁻. Oxidation of the anionic methylidyne complex with ferrocenium hexafluorophosphate generates the diamagnetic methylidyne complex (^FtbsL)Co₃(μ³–CH). The methylidyne ligand can be deprotonated with Li- or KN(SiMe₃)₂ to afford carbide complexes (^FtbsL)Co₃(μ⁴–C)Li(OEt₂) or [K(C₂₂₂)][(^FtbsL)Co₃(μ³–C)], respectively. Isotopic enrichment of the carbide with ¹³C reveals downfield-shifted ¹³C NMR chemical shifts (δ/ppm) of 389, Co₃(μ³–CH); 731, Co₃(μ⁴–CLi); and 769, Co₃(μ³–C)⁻; the latter of which is the most downfield resonance for a transition metal carbide reported to date.

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稳定碳化三钴团簇的合成

本文报道了阴离子型碳化三钴簇[(FtbsL)Co3(μ3-C)]−的合成和表征。碳化物配体的来源是磷酰化(R2MePCH2；R = Me, Ph)在全钴（II）簇（FtbsL）Co3（py）中取代吡啶，生成ylide加合物（FtbsL）Co3（CH2PMeR2）。脱质子反应生成阴离子二乙基化物团簇[(FtbsL)Co3(κ2-η1:η1 - (CH2)2PR2)]−，加热后MePR2消失，生成阴离子甲基苯胺团簇[(FtbsL)Co3(μ3-CH)]−。阴离子甲基醚配合物与六氟磷酸二茂铁氧化生成抗磁性甲基醚配合物（FtbsL）Co3（μ3-CH）。甲基炔配体可与Li-或KN(SiMe3)2脱质子生成碳化物配合物（FtbsL）Co3(μ4-C)Li（OEt2）或[K(C222)][(FtbsL)Co3(μ3-C)]。碳化物的13C同位素富集表明13C核磁共振下移的化学位移（δ/ppm）为389，Co3(μ3-CH)；731年,二氧化碳(μ4-CLi);769, Co3(μ3-C)−；后者是迄今为止报道的过渡金属碳化物中最常见的下场共振。

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

Journal of the American Chemical Society 化学-化学综合

CiteScore

24.40

自引率

6.00%

发文量

2398

审稿时长

1.6 months

期刊介绍： The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.