Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
7763219 | Polyhedron | 2018 | 13 Pages |
Abstract
The planned synthesis of hypervalent 10-P-3 and 10-As-3 compounds 1 and 2 from brominated bis(oxazoline) and bis(imine) NCN pincers via a lithiation/electrophilic quenching (with PnCl3; Pn = P or As)/reduction protocol resulted in unexpected findings and reactivity. Generation of bis(oxazoline)-ligated (NCN)PCl2 derivative CP resulted in an intramolecular SN2 reaction, leading to formation of ring-opened 3, which could be phenylated with PhMgBr to give 4. In solution, bis(imine)-based (NCN)PCl2 analogue DP displayed a complicated product mixture by 31P{1H} NMR spectroscopy, likely due to the presence of several ionic species and iminium-enamine tautomers, while the As derivative (DAs) was isolable and crystallized in a distorted square pyramidal geometry. Reduction of both derivatives of D with PMe3 did not afford the targeted 10-Pn-3 (Pn = P or As) species 2, but rather generated rare examples of dynamic bell-clappers.74
Keywords
Related Topics
Physical Sciences and Engineering
Chemistry
Inorganic Chemistry
Authors
Jakub Hyvl, Wesley Y. Yoshida, Curtis E. Moore, Arnold L. Rheingold, Matthew F. Cain,