Facile synthesis and bonding of 4-ferrocenyl-1,2,4-triazol-5-ylidene complexes
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F24%3A10490247" target="_blank" >RIV/00216208:11310/24:10490247 - isvavai.cz</a>
Result on the web
<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=LqflcMJH0U" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=LqflcMJH0U</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/d4dt01433b" target="_blank" >10.1039/d4dt01433b</a>
Alternative languages
Result language
angličtina
Original language name
Facile synthesis and bonding of 4-ferrocenyl-1,2,4-triazol-5-ylidene complexes
Original language description
Ferrocene-substituted carbenes have emerged as attractive, redox-active ligands. However, among the compounds studied to date, ferrocenylated 1,2,4-triazol-5-ylidenes, which are closely related to the archetypal imidazol-2-ylidenes, are still unknown. Here, we demonstrate that the triazolium salt [CHN(Me)NCHN(Fc)]I (2; Fc = ferrocenyl), obtained by alkylation of 4-ferrocenyl-4H-1,2,4-triazole (1) with MeI, reacts selectively with metal alkoxide/hydroxide precursors [(cod)Rh(OMe)]2 and [(IPr)Au(OH)] (cod = cycloocta-1,5-diene, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) to produce the ferrocene-substituted 1,2,4-triazol-5-ylidene complexes [(cod)RhI{CN(Me)NCHN(Fc)}] and [(IPr)Au{CN(Me)NCHN(Fc)}]I in good yields. The complexes were characterised by NMR and IR spectroscopy, mass spectrometry, cyclic voltammetry, and single-crystal X-ray diffraction analysis. Density function theory (DFT) calculations were used to rationalise the electrochemical behaviour of the carbene complexes and to elucidate the bonding situation in these compounds. An analysis using intrinsic bond orbitals (IBOs) revealed that the 1,2,4-triazol-5-ylidene ligand exerted a strong trans influence and showed a synergistic stabilisation by the negative inductive and positive π-donor effects of the nitrogen atoms adjacent to the carbene carbon atom; these effects were enhanced by conjugation with the CH=N bond at the exterior, similar to that in imidazol-2-ylidenes. Triazolium salt obtained by alkylation of 4-ferrocenyl-4H-1,2,4-triazole reacts smoothly with metal hydroxides and alkoxides to produce 4-ferrocenyl-1,2,4-triazol-5-ylidene complexes, whose bonding was studied experimentally and theoretically.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10402 - Inorganic and nuclear chemistry
Result continuities
Project
<a href="/en/project/GA23-06718S" target="_blank" >GA23-06718S: Rigid and functional ferrocene phosphines</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2024
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Dalton Transactions
ISSN
1477-9226
e-ISSN
1477-9234
Volume of the periodical
53
Issue of the periodical within the volume
27
Country of publishing house
GB - UNITED KINGDOM
Number of pages
9
Pages from-to
11445-11453
UT code for WoS article
001251357800001
EID of the result in the Scopus database
2-s2.0-85196726473