An α-diiminato germylene family: syntheses, structures, and reactivity towards C-C coupled digermylene and
Jingjing Liu1, Jianxuan Shang2, Jing Wei1
1Key Laboratory of Synthetic and Natural Functional Molecule of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710127, P. R. China. liay@nwu.edu.cn.
Abstract:
The synthesis and reactivity of a rigid α-diiminate ligand supported chlorogermylene 2 were demonstrated. The reaction of 2 with hydride donor K[BH(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(SiBuMe2)2. Halide abstraction with AlCl3 from 2 afforded a cationic germylene 5, and the reduction of 2 with potassium led to a C-C coupled digermylene 6via a radical coupling pathway. Hydrolysis of 2 in the presence of NHC ((Bu-NCH)2C:) gave digermylene oxide 7. DFT investigations of central GeII-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.
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