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Artikel (Publikationen im Open Access gefördert durch die UB)
Coinage Metal Complexes of the Carbenic Tautomer of a Conjugated Mesomeric Betaine Akin to Nitron
Abstract
This study was motivated by our recent observation that the analytical reagent Nitron (2) is an “instant carbene”, whose reaction with coinage metal salts MX afforded complexes of its carbenic tautomer 1,4-diphenyl-3-phenylamino-1,2,4-triazol-5-ylidene (2′). Our aim was to establish an alkyl homologue of 2 in order to achieve a carbenic tautomer of higher donicity. For this purpose 1-tert-butyl-4-methyl-1,2,4-triazol-4-ium-3-tert-butylaminide (6) was synthesized. Its reactions with MX afforded complexes of the carbenic tautomer 1-tert-butyl-3-tert-butylamino-4-methyl-1,2,4-triazol-5-ylidene (6′). With a stoichiometric ratio of 1:1 complexes of the type [MX(6′)] were obtained. A ratio of 2:1 furnished complexes of the type [MX(6′)2] or [M(6′)2]X. 6′ is a better σ-donor and less electrophilic than 2′ according to NMR spectroscopic data of 6H[BF4] and 6′ = Se, respectively, and IR spectroscopic data of [RhCl(6′)(CO)2] confirm that its net electron donor capacity is superior to that of 2′. A comparison of the complexes of 2′ and 6′ reveals two pronounced structural differences. [CuX(6′)2] (X = Cl, Br) exhibit more acute C‒Cu‒C bond angles than [CuX(2′)2]. In contrast to [CuCl(2′)], [CuCl(6′)] aggregates through Cu···Cu contacts of ca. 2.87 Å, compatible with cuprophilic interactions. These differences may be explained by the complementary steric requirements of the t-Bu and the Me substituent of 6′.
Citation
In: Molecules. - Basel : MDPI. - 2017, 22(7), 1133, 1-22Sponsorship
Gefördert durch den Publikationsfonds der Universität KasselCollections
Publikationen (Arbeitsgruppe Metallorganische Chemie)Artikel (Publikationen im Open Access gefördert durch die UB)
Citation
@article{urn:nbn:de:hebis:34-2018013154265,
author={Thie, Charlotte and Bruhn, Clemens and Leibold, Michael and Siemeling, Ulrich},
title={Coinage Metal Complexes of the Carbenic Tautomer of a Conjugated Mesomeric Betaine Akin to Nitron},
year={2017}
}
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2018-01-31T13:54:53Z 2018-01-31T13:54:53Z 2017-07-07 1420-3049 urn:nbn:de:hebis:34-2018013154265 http://hdl.handle.net/123456789/2018013154265 Gefördert durch den Publikationsfonds der Universität Kassel eng Urheberrechtlich geschützt https://rightsstatements.org/page/InC/1.0/ conjugated mesomeric betaine coinage metals copper crystal structure gold N-heterocyclic carbene silver 1,2,4-triazol-5-ylidene 500 Coinage Metal Complexes of the Carbenic Tautomer of a Conjugated Mesomeric Betaine Akin to Nitron Aufsatz This study was motivated by our recent observation that the analytical reagent Nitron (2) is an “instant carbene”, whose reaction with coinage metal salts MX afforded complexes of its carbenic tautomer 1,4-diphenyl-3-phenylamino-1,2,4-triazol-5-ylidene (2′). Our aim was to establish an alkyl homologue of 2 in order to achieve a carbenic tautomer of higher donicity. For this purpose 1-tert-butyl-4-methyl-1,2,4-triazol-4-ium-3-tert-butylaminide (6) was synthesized. Its reactions with MX afforded complexes of the carbenic tautomer 1-tert-butyl-3-tert-butylamino-4-methyl-1,2,4-triazol-5-ylidene (6′). With a stoichiometric ratio of 1:1 complexes of the type [MX(6′)] were obtained. A ratio of 2:1 furnished complexes of the type [MX(6′)2] or [M(6′)2]X. 6′ is a better σ-donor and less electrophilic than 2′ according to NMR spectroscopic data of 6H[BF4] and 6′ = Se, respectively, and IR spectroscopic data of [RhCl(6′)(CO)2] confirm that its net electron donor capacity is superior to that of 2′. A comparison of the complexes of 2′ and 6′ reveals two pronounced structural differences. [CuX(6′)2] (X = Cl, Br) exhibit more acute C‒Cu‒C bond angles than [CuX(2′)2]. In contrast to [CuCl(2′)], [CuCl(6′)] aggregates through Cu···Cu contacts of ca. 2.87 Å, compatible with cuprophilic interactions. These differences may be explained by the complementary steric requirements of the t-Bu and the Me substituent of 6′. open access In: Molecules. - Basel : MDPI. - 2017, 22(7), 1133, 1-22 Thie, Charlotte Bruhn, Clemens Leibold, Michael Siemeling, Ulrich doi:10.3390/molecules22071133
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