Bulky Bis-Guanidine Ligand Based Neutral and Cationic Zinc Alkyl, Halide, and Hydride Complexes: Synthesis, Characterization, and Catalytic Application

IF 3.3 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions Pub Date : 2025-09-16 DOI:10.1039/d4dt02907k

Rajata Kumar Sahoo, Sayantan Mukhopadhyay, Sagrika Rajput, Achintya Jana, Sharanappa Nembenna

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引用次数: 0

Abstract

The tetra-aryl substituted bis-guanidine ligand L(3H) (L(3H) = {(ArHN)(ArNH)-C=N-C=(NAr)(NHAr)}; Ar=2,6-iPr2-C6H3), was used for the synthesis of mononuclear zinc(II) alkyls [L(2H)ZnR, R = Me (Zn-1), Et (Zn-2)], iodide [L(2H)ZnI, (Zn-3)], hydride [L(2H)ZnH, (Zn-4)] complexes. Moreover, the reactions of Zn-1, Zn-2, and Zn-3 with [PhNMe2H]+ [B(C6F5)4]- yielded the biguanide zinc alkyls [L(3H)ZnR]+ [B(C6F5)4]-, R = Me (Zn-5), Et (Zn-6) and iodide [L(3H)ZnI]+ [B(C6F5)4]- (Zn-7) cationic compounds in good yields. All newly isolated and thermally stable zinc complexes (Zn-1 – Zn-7) were well characterized by multinuclear NMR (¹H, ¹³C{¹H}, with additional ¹¹B and ¹⁹F{¹H} for Zn-5 - Zn-7), HRMS, and single crystal X-ray diffraction studies. Moreover, the well-defined zinc iodide cation (Zn-7) [L(3H)ZnI]+ [B(C6F5)4]- was further used as a catalyst for the synthesis of cyanohydrin enol ether products (RCR’CNOSiMe3) by TMSCN addition in carbonyl compounds (RCOR’, R’ = alkyl/aryl) under mild reaction conditions.

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基于中性和阳离子锌烷基、卤化物和氢化物的大体积双胍配体：合成、表征和催化应用

四芳基取代双胍配体L(3H) (L(3H) = {(ArHN)(ArNH)-C=N-C=(NAr)(NHAr)}；Ar=2,6- ipr2 - c6h3)，用于合成单核锌（II）烷基[L(2H)ZnR, R = Me (Zn-1), Et (Zn-2)]，碘化物[L(2H)ZnI, (Zn-3)]，氢化物[L(2H)ZnH, (Zn-4)]配合物。此外，Zn-1、Zn-2和Zn-3与[PhNMe2H]+ [B(C6F5)4]-反应生成了双烷化锌烷基[L(3H)ZnR]+ [B(C6F5)4]-, R = Me (Zn-5), Et （Zn-6）和碘化物[L(3H)ZnI]+ [B(C6F5)4]- (Zn-7)阳离子化合物，收率较高。所有新分离的热稳定锌配合物（Zn-1 - Zn-7）均通过多核磁共振（¹H，¹³C{¹H}，外加Zn-5 - Zn-7的¹¹B和¹⁹F{¹H}）、HRMS和单晶x射线衍射进行了表征。此外，在温和的反应条件下，将定义明确的碘化锌阳离子（Zn-7） [L(3H)ZnI]+ [B(C6F5)4]-作为催化剂，在羰基化合物（RCR ', R ' =烷基/芳基）中加成TMSCN合成氰基醇烯醇醚产物（RCR ' cnosime3）。

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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.