Cluster-bound nitriles do not click with organic azides: Unexpected formation of imino complexes of the [Re63-Se) 8]2+ core-containing clusters

Xiaoyan Tu, Ethan Boroson, Huong Truong, Alvaro Muñoz-Castro, Ramiro Arratia-Pérez, Gary S. Nichol, Zhiping Zheng

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Abstract

The reactions of C6H5CH(CH3)N3 with nitrlle solvates of the [Re63-Se) 8]2+ core-containing cluster, [Re63-Se)8(PEt3)5-(MeCN)] 2+(1) and cis-[Re63-Se) 8(PEt3)4(MeCN)2]2+ (2), afforded the corresponding cationlc imino complexes [Re633-Se)8-(PEt3)5(PhN=CHCH 3)2+ (3) and cis-[Re63-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.

Original languageEnglish (US)
Pages (from-to)380-382
Number of pages3
JournalInorganic Chemistry
Volume49
Issue number2
DOIs
Publication statusPublished - Jan 18 2010

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ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

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