We found a match
Your institution may have access to this item. Find your institution then sign in to continue.
- Title
An Isolable Phosphinogermylyne as a Synthon of One-Coordinate GeI Radical.
- Authors
Dongmin Wang; Haonan Chen; Yuhao He; Xiaodan Chen; Li Zhang; Gengwen Tan
- Abstract
Reduction of chlorogermylene MsFluindtBth potassium graphite (KC8) afforded putative germylyne radical MsFluindtBu-Ge 2 as confirmed by electron paramagnetic resonance (EPR) spectroscopy. However, it slowly decayed via C--H bond activation at the fluorenyl moiety to yield a bis(germylene) 3 at room temperature. By using a Lewis base to stabilize the unoccupied p orbital at the GeI radical center, acyclic two-coordinate GeI radicals MsFluindtBu-Ge(IMe4) 4 (IMe4 = 1,3,4,5-tetramethyl-imidazolin-2-ylidene), MsFluindtBu-Ge(IiPr) 5 (IiPr = 1,3-diisopropyl-4,5-dimethyl-imidazolin-2-ylidene), MsFluindtBu-Ge(PMe3) 6 were isolated in crystalline forms. The unpaired electron in 4--6 mainly resides at the Ge 4p orbital as revealed by EPR spectroscopic studies and theoretical calculations. Interestingly, facile ligand exchange of PMe3 in 6 with IMe4 and IiPr was observed to afford 4 and 5, respectively. Moreover, phosphinogermylyne 6 reacted with PhEEPh (E = S, Se), 4-tetrabutylphenylacetylene (Ar'CCH), [CpMo(CO)3]2 and nBu3SnH to furnish germylenes MsFluindtBu-GeEPh (E = S 7, Se 8), MsFluindtBu-GeCH=CHAr' 9, a germylyne complex MsFluindtBu-Ge=Mo(CO)2Cp 10 and a Ge(IV) compound MsFluindtBu-GeH2SnnBu3 11, respectively. The reactivity studies demonstrate that 6 can act as a synthon of one-coordinate germylyne radical attributing to labile coordination of trimethylphosphine.
- Subjects
RADICALS (Chemistry); ELECTRON paramagnetic resonance; LEWIS bases; GERMYLENES; RADICALS
- Publication
Chinese Journal of Chemistry, 2024, Vol 42, Issue 7, p736
- ISSN
1001-604X
- Publication type
Article
- DOI
10.1002/cjoc.202300581