NDLI: Geometrically Specific Imino Complexes of the $[Re_{6}(μ_{3}-Se)_{8}]^{2+}$ Core-Containing Clusters

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Geometrically Specific Imino Complexes of the $[Re_{6}(μ_{3}-Se)_{8}]^{2+}$ Core-Containing Clusters

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Zheng, Zhiping Tu, Xiaoyan Arratia-pérez, Ramiro Truong, Huong Alster, Eli Muñoz-castro, Alvaro Nichol, Gary S.
Description	Author Affiliation: Tu X ( Department of Chemistry, University of Arizona, Tucson, AZ 85721, USA.)
Abstract	The reactions of nitrile complexes of the $[Re_{6}(μ_{3}-Se)_{8}]^{2+}$ core-containing clusters, $[Re_{6}(μ_{3}-Se)_{8}(PEt_{3})_{n}(CH_{3}CN)_{6−n}]^{2+}$ [n=5 (1); n=4, cis- (2) and trans- (3); n=0 (4)], with organic azides $C_{6}H_{5}CH(CH_{3})N_{3}$ and $C_{6}H_{5}CH_{2}N_{3}$ produced the corresponding cationic imino complexes of the general formula $[Re_{6}(μ_{3}-Se)_{8}(PEt_{3})_{n}(L)_{6−n}]^{2+}$ $[L=PhNCHCH_{3}:$ n=5 (5); n=4, cis- (6) and trans- (7); n=0 (8) and L=HNCHPh: n=5 (9); n=4, cis- (10) and trans- (11)]. These novel complexes were characterized by NMR spectroscopy $(^{1}H$ and $^{31}P)$ and single-crystal X-ray diffraction. A mechanism involving the migration of one of the groups on the azido α-C atom to the α-N atom of the azido complex, concerted with the photo-expulsion of $N_{2},$ was invoked to rationalize the formation of the imino complexes. Density functional theory (DFT) calculations indicated that due to the coordination with and activation by the cluster core, the energy of the electronic transition responsible for the photo-decomposition of a cluster-bound azide is much reduced with respect to its pure organic counterpart. The observed geometric specificity was rationalized by using the calculated and optimized preferred ground-state conformation of the cluster-azido intermediates.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	2
Volume Number	17
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2011-01-10
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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