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A digermylene (LGeI–GeIL) on an N-heterocyclic carbene–fluorenyl hybrid ligand (L) and its oxidation by TEMPO and Ph2E2 (E = S, Se).

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Title: A digermylene (LGeI–GeIL) on an N-heterocyclic carbene–fluorenyl hybrid ligand (L) and its oxidation by TEMPO and Ph2E2 (E = S, Se).
Authors: Mondal, Sumana1 (AUTHOR), Sarkar, Subham1,2 (AUTHOR), Mandal, Chhotan1 (AUTHOR), Mallick, Dibyendu2 (AUTHOR) dibyendu.chem@presiuniv.ac.in, Mukherjee, Debabrata1 (AUTHOR) d.mukherjee@iiserkol.ac.in
Source: Dalton Transactions: An International Journal of Inorganic Chemistry. 11/21/2025, Vol. 54 Issue 43, p16006-16013. 8p.
Subjects: Oxidation, Germanium compounds, Chemical species, Carbenes, Fluorene compounds, Oxidizing agents
Abstract: A hybrid N-heterocyclic carbene (NHC)–fluorenyl ligand (L) supported GeIICl complex ([LGeCl]; 1) has been made from GeCl2(dioxane) and [LK]n. Compound 1 is reduced by Jones' Mg I2 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. Compound 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. Overoxidation of 2 by Ph2Se2 to give a mixed-valent trinuclear species [{(PhSe)2GeII}2(μ-L)2GeIV(SePh)2] (6) is also noted. Besides, precursor 1 is converted into [LGeMe] (7) and [LGeOSiPh3] (8) by treating it with MeMgBr and KOSiPh3, respectively. However, none of these compounds leads to a desired [LGeH] species. Also, interestingly, Cl-abstraction from 1 by AgSbF6 fails and it rather forms a 2 : 1 adduct [(LGeCl)2Ag][SbF6] (9). [ABSTRACT FROM AUTHOR]
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Abstract:A hybrid N-heterocyclic carbene (NHC)–fluorenyl ligand (L) supported GeIICl complex ([LGeCl]; 1) has been made from GeCl2(dioxane) and [LK]n. Compound 1 is reduced by Jones' Mg I2 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. Compound 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. Overoxidation of 2 by Ph2Se2 to give a mixed-valent trinuclear species [{(PhSe)2GeII}2(μ-L)2GeIV(SePh)2] (6) is also noted. Besides, precursor 1 is converted into [LGeMe] (7) and [LGeOSiPh3] (8) by treating it with MeMgBr and KOSiPh3, respectively. However, none of these compounds leads to a desired [LGeH] species. Also, interestingly, Cl-abstraction from 1 by AgSbF6 fails and it rather forms a 2 : 1 adduct [(LGeCl)2Ag][SbF6] (9). [ABSTRACT FROM AUTHOR]
ISSN:14779226
DOI:10.1039/d5dt02074c