An α-diiminato germylene family: syntheses, structures, and reactivity towards C-C coupled digermylene and digermylene oxide

The synthesis and reactivity of a rigid α-diiminate ligand supported chlorogermylene 2 were demonstrated. The reaction of 2 with hydride donor K[BH( s Bu) 3 ] yielded a hydride addition product, a five-membered 6π-aromatic germylene 3 . A nonaromatic germylene 4 was produced by dehydrochlorination o...

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Veröffentlicht in:Dalton transactions : an international journal of inorganic chemistry 2022-06, Vol.51 (22), p.8671-8679
Hauptverfasser: Liu, Jingjing, Shang, Jianxuan, Wei, Jing, Gao, Fangfang, Hou, Lei, Zeng, Fanlong, Li, Anyang, Wang, Wenyuan
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Sprache:eng
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Zusammenfassung:The synthesis and reactivity of a rigid α-diiminate ligand supported chlorogermylene 2 were demonstrated. The reaction of 2 with hydride donor K[BH( s Bu) 3 ] yielded a hydride addition product, a five-membered 6π-aromatic germylene 3 . A nonaromatic germylene 4 was produced by dehydrochlorination of 2 with KN(Si t BuMe 2 ) 2 . Halide abstraction with AlCl 3 from 2 afforded a cationic germylene 5 , and the reduction of 2 with potassium led to a C-C coupled digermylene 6 via a radical coupling pathway. Hydrolysis of 2 in the presence of NHC (( t Bu-NCH) 2 C:) gave digermylene oxide 7 . DFT investigations of central Ge II -rings in molecules 3-5 provided the details of frontier molecular orbitals. The energy level of the lone pair on the Ge atom in 3 is slightly higher than that in 4 , indicating that 3 is the stronger σ-donor than 4 . Digermylene 6 and its diastereoisomer 6a feature trans -bent and gauche -bent configurations along their axially chiral C-C bonds, respectively. The conformational and cis-trans isomerism was observed by the isolation of crystal structures 7 and 7a because of intramolecular steric hindrance. The synthesis and reactivity of a germylene chloride 2 stabilized by a rigid α-diiminate ligand was systematically explored to afford a new family of germylenes, which bonding nature was revealed by their XRD structures and DFT calculations.
ISSN:1477-9226
1477-9234
DOI:10.1039/d2dt00981a