Concurrent stabilization of π-donor and π-acceptor ligands in aromatized and dearomatized pincer [(PNN)Re(CO)(O)2] complexes.
Angew Chem Int Ed Engl
; 53(32): 8320-2, 2014 Aug 04.
Article
en En
| MEDLINE
| ID: mdl-24888243
ABSTRACT
Aromatized cationic [(PNN)Re(πâ
acid)(O)2](+) (1) and dearomatized neutral [(PNN*)Re(πâ
acid)(O)2] (2) complexes (where πâ
acid=CO (a), tBuNC (b), or (2,6-Me2)PhNC (c)), possessing both π-donor and π-acceptor ligands, have been synthesized and fully characterized. Reaction of [(PNN)Re(O)2](+) (4) with lithiumhexamethyldisilazide (LiHMDS) yield the dearomatized [(PNN*)Re(O)2] (3). Complexes 1 and 2 are prepared from the reaction of 4 and 3, respectively, with CO or isocyanides. Single-crystal X-ray structures of 1 a and 1 b show the expected trans-dioxo structure, in which the oxo ligands occupy the axial positions and the π-acidic ligand occupies the equatorial plane in an overall octahedral geometry about the rhenium(V) center. DFT studies revealed the stability of complexes 1 and 2 arises from a π-backbonding interaction between the d(xy) orbital of rhenium, the πâ
orbital of the oxo ligands, and the π*â
orbital of CO/isocyanide.
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Colección:
01-internacional
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MEDLINE
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En
Revista:
Angew Chem Int Ed Engl
Año:
2014
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Article