Germanium-Functionalized Tri- and Tetraphosphido Cobalt Complexes

IF 2.9 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2025-07-31 DOI:10.1021/acs.organomet.5c00214

Karolina Trabitsch, Sebastian Hauer, Gábor Balázs, Jan J. Weigand and Robert Wolf*,

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Abstract

We report the synthesis of germanium-containing polyphosphorus ligands in transition metal complexes through the insertion of an Ar′GeCl unit into a P–P bond of polyphosphorus ligands (Ar′ = 2,6-(2,6-iPr₂C₆H₃)₂-C₆H₃). Germatetraphosphido complexes [(L)Co(η⁴-P₄GeAr′)] (1a: L = PHDI; 1b: L = Ar*BIAN; PHDI = bis(2,6-diisopropylphenyl)phenanthrene-9,10-diimine, Ar*BIAN = 1,2-bis(arylimino)acenaphthene, aryl = 2,6-dibenzhydryl-4-isopropylphenyl) were obtained by treatment of the anionic cyclo-P₄ complexes [K(18c-6)][(L)Co(η⁴-P₄)] with [Ar′GeCl]₂ . Similar reactions of the cyclo-P₃ complexes [cat][(L)Co(CN)(η³-P₃)] ([cat]⁺ = [nBu₄N]⁺ or [K(18c-6)]⁺) afforded [cat][(L)Co(η³-P₃GeAr′Cl)(CN)] (2a: L = PHDI, [cat]⁺ = [nBu₄N]⁺; 2b: L = Ar*BIAN, [cat]⁺ = [K(18c-6)]⁺). The reactivity of 2a was studied toward group 14 electrophiles, yielding neutral germatriphosphido analogues [(PHDI)Co(η³-P₃GeAr′Cl)(CNER₃)] (3-ER₃, ER₃ = CPh₃, Si(iPr)₃). Furthermore, treatment of 2a with the group 13 Lewis acid GaCl₃ gave [nBu₄N][(PHDI)Co(η³-P₃GeAr′Cl)(CNGaCl₃)] (4-Ga) and [(PHDI)Co(η³-P₂Ge(PAr′))(CNGaCl₃)] (5-Ga), which features a remarkable P₃GeAr′ ligand. Compounds 1–5 were isolated as crystalline materials and characterized by single-crystal X-ray diffraction and multinuclear NMR spectroscopy supported by DFT calculations.

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锗功能化三磷和四磷钴配合物

我们报道了在过渡金属配合物中通过在多磷配体的P-P键上插入Ar ' gecl单元合成含锗多磷配体（Ar ' = 2,6-(2,6- ipr2c6h3)2- c6h3）。杂磷配合物[(L)Co(η - 4- p4gear ')] (1a: L = PHDI；1b: L = Ar*BIAN；用[Ar 'GeCl]2处理阴离子环- p4配合物[K(18c-6)][(L)Co（η - p4)]得到PHDI =二（2,6-二异丙基苯基）菲-9,10-二亚胺，Ar*BIAN = 1,2-二（芳基）苊，aryl = 2,6-二苯并基-4-异丙基苯基）。环- p3配合物[cat][(L)Co(CN)(η - 3- p3)] （[cat]+ = [nBu4N]+或[K(18c-6)]+）的类似反应产生[cat][(L)Co(η - 3- p3gear 'Cl)(CN)] (2a: L = PHDI, [cat]+ = [nBu4N]+；b: L = Ar*BIAN, [cat]+ = [K(18c-6)]+)。研究了2a对14族亲电试剂的反应性，得到中性的母质磷酸类似物[(PHDI)Co(η3-P3GeAr’cl)(CNER3)] （3-ER3, ER3 = CPh3, Si(iPr)3）。此外，用13组Lewis酸GaCl3处理2a得到[nBu4N][(PHDI)Co(η - 3-P3GeAr ' cl)(CNGaCl3)] （4-Ga）和[(PHDI)Co(η - 3- p2ge (PAr ‘))(CNGaCl3)] (5-Ga)，其P3GeAr ’配体具有显著的特征。化合物1-5被分离为晶体材料，并通过单晶x射线衍射和DFT计算支持的多核磁共振波谱进行了表征。

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.