A digermylene (LGe <sup>I</sup> –Ge <sup>I</sup> L) on an N-heterocyclic carbene–fluorenyl hybrid ligand (L) and its oxidation by TEMPO and Ph <sub>2</sub> E <sub>2</sub> (E = S, Se)

A hybrid N-heterocyclic carbene (NHC)-fluorenyl ligand (L) supported Ge<sup>II</sup>Cl complex ([LGeCl]; 1) has been made from GeCl<sub>2</sub>(dioxane) and [LK]<sub><i>n</i></sub>. Compound 1 is reduced by Jones' MgI2 dimer [(<sup>Mes</sup>NacnacMg)<sub>2</sub>] (<sup>Mes</sup>Nacnac = [{(Mes)NCMe}<sub>2</sub>CH]<sup>-</sup>; Mes = 2,4,6-Me<sub>3</sub>-C<sub>6</sub>H<sub>2</sub>) to give the digermylene [LGe<sup>I</sup>-Ge<sup>I</sup>L] (2) with a <i>gauche</i>-bent conformation. Compound 2 is oxidized by TEMPO (2,2,6,6-tetramethylpiperidinyloxy) and Ph<sub>2</sub>E<sub>2</sub> (E = S, Se) to give [LGe(TEMPO)] (3) and [LGeEPh] (E = S (4), Se (5)), respectively. Overoxidation of 2 by Ph<sub>2</sub>Se<sub>2</sub> to give a mixed-valent trinuclear species [{(PhSe)<sub>2</sub>Ge<sup>II</sup>}<sub>2</sub>(μ-L)<sub>2</sub>Ge<sup>IV</sup>(SePh)<sub>2</sub>] (6) is also noted. Besides, precursor 1 is converted into [LGeMe] (7) and [LGeOSiPh<sub>3</sub>] (8) by treating it with MeMgBr and KOSiPh<sub>3</sub>, respectively. However, none of these compounds leads to a desired [LGeH] species. Also, interestingly, Cl-abstraction from 1 by AgSbF<sub>6</sub> fails and it rather forms a 2 : 1 adduct [(LGeCl)<sub>2</sub>Ag][SbF<sub>6</sub>] (9).

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Journal
Dalton Transactions
Published
2025-01-01
DOI
https://doi.org/10.1039/d5dt02074c
Primary Topic
Synthesis and characterization of novel inorganic/organometallic compounds
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article
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article

A digermylene (LGe I –Ge I L) on an N-heterocyclic carbene–fluorenyl hybrid ligand (L) and its oxidation by TEMPO and Ph 2 E 2 (E = S, Se)

Dibyendu Mallick, Sumana Mondal, Chhotan Mandal, Debabrata Mukherjee et al.
Dalton Transactions
Synthesis and characterization of novel inorganic/organometallic compounds
article

A digermylene (LGe I –Ge I L) on an N-heterocyclic carbene–fluorenyl hybrid ligand (L) and its oxidation by TEMPO and Ph 2 E 2 (E = S, Se)

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

Abstract

A hybrid N-heterocyclic carbene (NHC)-fluorenyl ligand (L) supported Ge<sup>II</sup>Cl complex ([LGeCl]; 1) has been made from GeCl<sub>2</sub>(dioxane) and [LK]<sub><i>n</i></sub>. Compound 1 is reduced by Jones' MgI2 dimer [(<sup>Mes</sup>NacnacMg)<sub>2</sub>] (<sup>Mes</sup>Nacnac = [{(Mes)NCMe}<sub>2</sub>CH]<sup>-</sup>; Mes = 2,4,6-Me<sub>3</sub>-C<sub>6</sub>H<sub>2</sub>) to give the digermylene [LGe<sup>I</sup>-Ge<sup>I</sup>L] (2) with a <i>gauche</i>-bent conformation. Compound 2 is oxidized by TEMPO (2,2,6,6-tetramethylpiperidinyloxy) and Ph<sub>2</sub>E<sub>2</sub> (E = S, Se) to give [LGe(TEMPO)] (3) and [LGeEPh] (E = S (4), Se (5)), respectively. Overoxidation of 2 by Ph<sub>2</sub>Se<sub>2</sub> to give a mixed-valent trinuclear species [{(PhSe)<sub>2</sub>Ge<sup>II</sup>}<sub>2</sub>(μ-L)<sub>2</sub>Ge<sup>IV</sup>(SePh)<sub>2</sub>] (6) is also noted. Besides, precursor 1 is converted into [LGeMe] (7) and [LGeOSiPh<sub>3</sub>] (8) by treating it with MeMgBr and KOSiPh<sub>3</sub>, respectively. However, none of these compounds leads to a desired [LGeH] species. Also, interestingly, Cl-abstraction from 1 by AgSbF<sub>6</sub> fails and it rather forms a 2 : 1 adduct [(LGeCl)<sub>2</sub>Ag][SbF<sub>6</sub>] (9).

Dalton TransactionsVol. 54(43)
Indian Institute of Science Education and Research Kolkata (IN), Presidency University (IN)
Department of Science and Technology, Ministry of Science and Technology, India, Indian Institute of Science Education and Research Pune, Indian Institute of Technology Kharagpur, Indian Institute of Science Education and Research Mohali, Indian Institute of Science Education and Research Kolkata, Science and Engineering Research Board
Openalex Percentile: Top 78%
Synthesis and characterization of novel inorganic/organometallic compounds
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