Alumanyl-Samarium(II): Synthesis, Characterization, and Reactivity Studies.
J Am Chem Soc
; 146(11): 7204-7209, 2024 Mar 20.
Article
in En
| MEDLINE
| ID: mdl-38505938
ABSTRACT
Metal-metal bonded species involving lanthanides are intriguing but rare. The recently reported salt metathesis reaction of an Al anion and SmI2(thf)2 yields novel heterometallic compound possessing two distinctive Al-Sm bonds. Although the Al-Sm bonds were considerably long [3.518(1) and 3.543(1) Å], DFT calculations indicated polar character of the Alδ--Smδ+ bonds. This is the first example of lanthanide species containing X-type Al ligands. Reactivity studies have demonstrated that the introduction of Sm(II) produces unique reactivity. The reaction with carbodiimide led to an insertion of carbodiimide into the Al-Sm bonds and reductive coupling of carbodiimide to create an oxalamidinate moiety, facilitated by Sm(II). Exposure of the Al-Sm-Al complex toward ethylene furnished a Sm(II) salt of anionic aluminacyclopropane that was spontaneously isomerized to a 1,4-dialuminacyclohexane derivative. The important role of Sm(II) to facilitate the ring expansion through an alkyl-relay mechanism was elucidated by DFT calculations.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
J Am Chem Soc
Year:
2024
Document type:
Article
Affiliation country:
Japan