Cluster-Bound Nitriles Do Not Click with Organic Azides: Unexpected Formation of Imino Complexes of the [Re 6 (μ 3 -Se) 8 ] 2+ Core-Containing Clusters
2009; American Chemical Society; Volume: 49; Issue: 2 Linguagem: Inglês
10.1021/ic902251z
ISSN1520-510X
AutoresXiaoyan Tu, Ethan Boroson, Huong Truong, Àlvaro Muñoz-Castro, Ramiro Arratia‐Pérez, S. Nichol Gary, Zhiping Zheng,
Tópico(s)Catalytic Cross-Coupling Reactions
ResumoThe reactions of C6H5CH(CH3)N3 with nitrile solvates of the [Re6(μ3-Se)8]2+ core-containing cluster, [Re6(μ3-Se)8(PEt3)5(MeCN)]2+(1) and cis-[Re6(μ3-Se)8(PEt3)4(MeCN)2]2+ (2), afforded the corresponding cationic imino complexes [Re6(μ3-Se)8(PEt3)5(PhN═CHCH3)]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 concerted 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.
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