Phosphorescent complexes of {Mo 6 I 8 } 4+ with triazolates: [2+3] cycloaddition of alkynes to [Mo 6 I 8 (N 3 ) 6 ] 2

(Bu 4 N) 2 [Mo 6 I 8 (N 3 ) 6 ], prepared in a clean high-yield reaction from (Bu 4 N) 2 [Mo 6 I 8 (CH 3 COO) 6 ] and Me 3 SiN 3 , undergoes [3+2] cycloaddition with CH 3 O(O)CC(O)OCH 3 with the formation of a novel hexakis(triazolate) complex, (Bu 4 N) 2 [Mo 6 I 8 (N 3 C 2 (COOCH 3 ) 2 ) 6 ] with...

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Bibliographic Details
Published in:New journal of chemistry 2020-12, Vol.44 (47), p.20620-20625
Main Authors: Mironova, Alina D., Mikhailov, Maksim A., Brylev, Konstantin A., Gushchin, Artem L., Sukhikh, Taisiya S., Sokolov, Maxim N.
Format: Article
Language:English
Subjects:
Alkynes
Crystallography
Cycloaddition
Infrared analysis
Isomers
Mass spectrometry
NMR
Nuclear magnetic resonance
Oxidation
Phosphorescence
Photoexcitation
Silver chloride
X ray analysis
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Summary:(Bu 4 N) 2 [Mo 6 I 8 (N 3 ) 6 ], prepared in a clean high-yield reaction from (Bu 4 N) 2 [Mo 6 I 8 (CH 3 COO) 6 ] and Me 3 SiN 3 , undergoes [3+2] cycloaddition with CH 3 O(O)CC(O)OCH 3 with the formation of a novel hexakis(triazolate) complex, (Bu 4 N) 2 [Mo 6 I 8 (N 3 C 2 (COOCH 3 ) 2 ) 6 ] with symmetrically coordinated 4,5-di(carbmethoxy)triazol-2-yl ligands. The product was characterized by X-ray analysis, NMR, IR and ESI-mass spectrometry. It undergoes a quasi reversible oxidation in CH 3 CN at E 1/2 = 1.36 V ( vs. Ag/AgCl) and is red-light emissive upon UV photoexcitation. Reaction with methylpropiolate also yields a corresponding hexakis(triazolate) complex, [Mo 6 I 8 (N 3 C 2 H(COOCH 3 )) 6 ] 2− , which exists as a 1 : 1 mixture of two isomers. Alkynes that lacking strongly electron-withdrawing substituents fail to undergo the cycloaddition reaction.
ISSN:1144-0546
1369-9261
DOI:10.1039/D0NJ04259E