The reactions of C6H5CH(CH3)N3 with nitrlle solvates of the [Re6(μ3-Se) 8]2+ core-containing cluster, [Re6(μ 3-Se)8(PEt3)5-(MeCN)] 2+(1) and cis-[Re6(μ3-Se) 8(PEt3)4(MeCN)2]2+ (2), afforded the corresponding cationlc imino complexes [Re6(μ 33-Se)8-(PEt3)5(PhN=CHCH 3)2+ (3) and cis-[Re6(μ3-Se) 8(PEt3)4(PhN= CHCH3) 2]2+ (4), respectively. Both compounds were spectroscopically and crystallographically characterized. A mechanism involving a 1,2-shift of one of the groups on the azido α-C atom of the cluster-azide intermediate conceited with the photoexpulsion of dinitrogen of the azido ligand is invoked to rationalize the formation of the imino complexes. Density functional theory calculations showed that a cluster-to-ligand transition was responsible for the absorption that promotes the photodecomposition of the cluster-azide complex.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry