Abstract
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.
Original language | English (US) |
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Pages (from-to) | 380-382 |
Number of pages | 3 |
Journal | Inorganic Chemistry |
Volume | 49 |
Issue number | 2 |
DOIs | |
State | Published - Jan 18 2010 |
Externally published | Yes |
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
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Dive into the research topics of 'Cluster-bound nitriles do not click with organic azides: Unexpected formation of imino complexes of the [Re6(μ3-Se) 8]2+ core-containing clusters'. Together they form a unique fingerprint.Datasets
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CCDC 801296: Experimental Crystal Structure Determination
Tu, X. (Creator), Boroson, E. (Creator), Truong, H. (Creator), Muñoz-Castro, A. (Contributor), Arratia-Pérez, R. (Contributor), Nichol, G. S. (Creator) & Zheng, Z. (Creator), Cambridge Crystallographic Data Centre, 2011
DOI: 10.5517/ccvwt8s, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccvwt8s&sid=DataCite
Dataset
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CCDC 801297: Experimental Crystal Structure Determination
Tu, X. (Creator), Boroson, E. (Creator), Truong, H. (Creator), Muñoz-Castro, A. (Contributor), Arratia-Pérez, R. (Contributor), Nichol, G. S. (Creator) & Zheng, Z. (Creator), Cambridge Crystallographic Data Centre, 2011
DOI: 10.5517/ccvwt9t, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccvwt9t&sid=DataCite
Dataset