n -杂环羰基-芴基杂化配体(L)上的二二甲苯（LGeI -GeIL）及其在TEMPO和Ph2E2 （E = S, Se）中的氧化作用

IF 3.3 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions Pub Date : 2025-09-30 DOI:10.1039/d5dt02074c

Sumana Mondal, Subham Sarkar, Chhotan Mandal, Dibyendu Mallick, Debabrata Mukherjee

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引用次数: 0

摘要

以GeCl2（二恶烷）和[LK]n为原料，合成了n -杂环碳(NHC)-芴基配体(L)负载的杂化GeIICl配合物（[lecl]; 1）。1被Jones ' MgI2二聚体[(MesNacnacMg)2]还原(mesnacnacc = [{(Mes)NCMe}2CH]─；Mes = 2,4,6- me3 - c6h2)得到具有扭扭弯曲构象的二二甲苯[LGeI-GeIL](2)。2分别被TEMPO（2,2,6,6-四甲基胡椒酰氧基）和Ph2E2 （E = S, Se）氧化得到[LGe(TEMPO)](3)和[LGeEPh] (E = S (4), Se(5)]。还注意到2被Ph2Se2过度氧化为混合价三核物质[{(PhSe)2GeII2(μ-L)2GeIV(SePh)2](6)。前驱体1经MeMgBr和KOSiPh3处理后分别转化为[LGeMe](7)和[LGeOSiPh3](8)。然而，它们都不能产生理想的[LGeH]物种。同样有趣的是，AgSbF6从1中提取cl失败，它们形成2:1加合物[(lecl]2Ag]SbF6(9)。

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A Digermylene (LGeI -GeIL) on a N-Heterocyclic Carbene-Fluorenyl Hybrid Ligand (L) and its Oxidation by TEMPO and Ph2E2 (E = S, Se)

A hybrid N-heterocyclic carbene (NHC)-fluorenyl ligand (L) supported GeIICl complex ([LGeCl]; 1) is made from GeCl2(dioxane) and [LK]n. 1 is reduced by Jones’ MgI2 dimer [(MesNacnacMg)2] (MesNacnac = [{(Mes)NCMe}2CH]─; Mes = 2,4,6-Me3-C6H2) to give the digermylene [LGeI-GeIL] (2) with a gauche-bent conformation. 2 is oxidized by TEMPO (2,2,6,6-tetramethylpiperidinyloxy) and Ph2E2 (E = S, Se) to give [LGe(TEMPO)] (3) and [LGeEPh] (E = S (4), Se (5)], respectively. An overoxidation of 2 by Ph2Se2 to a mixed valent trinuclear species [{(PhSe)2GeII2(μ-L)2GeIV(SePh)2] (6) is also noted. Besides, the precursor 1 is converted to [LGeMe] (7) and [LGeOSiPh3] (8) by treating with MeMgBr and KOSiPh3, respectively. However, none of them lead to a desired [LGeH] species. Also interestingly, Cl-abstraction from 1 by AgSbF6 fails and they rather form a 2:1 adduct [(LGeCl]2Ag]SbF6 (9).

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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.