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Polymerization Isomerism in Co-M (M = Cu, Ag, Au) Carbonyl Clusters: Synthesis, Structures and Computational Investigation

The reaction of [Co(CO)(4)](−) (1) with M(I) compounds (M = Cu, Ag, Au) was reinvestigated unraveling an unprecedented case of polymerization isomerism. Thus, as previously reported, the trinuclear clusters [M{Co(CO)(4)}(2)](−) (M = Cu, 2; Ag, 3; Au, 4) were obtained by reacting 1 with M(I) in a 2:1...

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Autores principales: Cesari, Cristiana, Berti, Beatrice, Calcagno, Francesco, Femoni, Cristina, Garavelli, Marco, Iapalucci, Maria Carmela, Rivalta, Ivan, Zacchini, Stefano
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7998641/
https://www.ncbi.nlm.nih.gov/pubmed/33799629
http://dx.doi.org/10.3390/molecules26061529
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author Cesari, Cristiana
Berti, Beatrice
Calcagno, Francesco
Femoni, Cristina
Garavelli, Marco
Iapalucci, Maria Carmela
Rivalta, Ivan
Zacchini, Stefano
author_facet Cesari, Cristiana
Berti, Beatrice
Calcagno, Francesco
Femoni, Cristina
Garavelli, Marco
Iapalucci, Maria Carmela
Rivalta, Ivan
Zacchini, Stefano
author_sort Cesari, Cristiana
collection PubMed
description The reaction of [Co(CO)(4)](−) (1) with M(I) compounds (M = Cu, Ag, Au) was reinvestigated unraveling an unprecedented case of polymerization isomerism. Thus, as previously reported, the trinuclear clusters [M{Co(CO)(4)}(2)](−) (M = Cu, 2; Ag, 3; Au, 4) were obtained by reacting 1 with M(I) in a 2:1 molar ratio. Their molecular structures were corroborated by single-crystal X-ray diffraction (SC-XRD) on isomorphous [NEt(4)][M{Co(CO)(4)}(2)] salts. [NEt(4)](3)represented the first structural characterization of 3. More interestingly, changing the crystallization conditions of solutions of 3, the hexanuclear cluster [Ag(2){Co(CO)(4)}(4)](2−) (5) was obtained in the solid state instead of 3. Its molecular structure was determined by SC-XRD as Na(2)(5)·C(4)H(6)O(2), [PPN](2)(5)·C(5)H(12) (PPN = N(PPh(3))(2)](+)), [NBu(4)](2)(5) and [NMe(4)](2)(5) salts. 5 may be viewed as a dimer of 3 and, thus, it represents a rare case of polymerization isomerism (that is, two compounds having the same elemental composition but different molecular weights) in cluster chemistry. The phenomenon was further studied in solution by IR and ESI-MS measurements and theoretically investigated by computational methods. Both experimental evidence and density functional theory (DFT) calculations clearly pointed out that the dimerization process occurs in the solid state only in the case of Ag, whereas Cu and Au related species exist only as monomers.
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spelling pubmed-79986412021-03-28 Polymerization Isomerism in Co-M (M = Cu, Ag, Au) Carbonyl Clusters: Synthesis, Structures and Computational Investigation Cesari, Cristiana Berti, Beatrice Calcagno, Francesco Femoni, Cristina Garavelli, Marco Iapalucci, Maria Carmela Rivalta, Ivan Zacchini, Stefano Molecules Article The reaction of [Co(CO)(4)](−) (1) with M(I) compounds (M = Cu, Ag, Au) was reinvestigated unraveling an unprecedented case of polymerization isomerism. Thus, as previously reported, the trinuclear clusters [M{Co(CO)(4)}(2)](−) (M = Cu, 2; Ag, 3; Au, 4) were obtained by reacting 1 with M(I) in a 2:1 molar ratio. Their molecular structures were corroborated by single-crystal X-ray diffraction (SC-XRD) on isomorphous [NEt(4)][M{Co(CO)(4)}(2)] salts. [NEt(4)](3)represented the first structural characterization of 3. More interestingly, changing the crystallization conditions of solutions of 3, the hexanuclear cluster [Ag(2){Co(CO)(4)}(4)](2−) (5) was obtained in the solid state instead of 3. Its molecular structure was determined by SC-XRD as Na(2)(5)·C(4)H(6)O(2), [PPN](2)(5)·C(5)H(12) (PPN = N(PPh(3))(2)](+)), [NBu(4)](2)(5) and [NMe(4)](2)(5) salts. 5 may be viewed as a dimer of 3 and, thus, it represents a rare case of polymerization isomerism (that is, two compounds having the same elemental composition but different molecular weights) in cluster chemistry. The phenomenon was further studied in solution by IR and ESI-MS measurements and theoretically investigated by computational methods. Both experimental evidence and density functional theory (DFT) calculations clearly pointed out that the dimerization process occurs in the solid state only in the case of Ag, whereas Cu and Au related species exist only as monomers. MDPI 2021-03-11 /pmc/articles/PMC7998641/ /pubmed/33799629 http://dx.doi.org/10.3390/molecules26061529 Text en © 2021 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Cesari, Cristiana
Berti, Beatrice
Calcagno, Francesco
Femoni, Cristina
Garavelli, Marco
Iapalucci, Maria Carmela
Rivalta, Ivan
Zacchini, Stefano
Polymerization Isomerism in Co-M (M = Cu, Ag, Au) Carbonyl Clusters: Synthesis, Structures and Computational Investigation
title Polymerization Isomerism in Co-M (M = Cu, Ag, Au) Carbonyl Clusters: Synthesis, Structures and Computational Investigation
title_full Polymerization Isomerism in Co-M (M = Cu, Ag, Au) Carbonyl Clusters: Synthesis, Structures and Computational Investigation
title_fullStr Polymerization Isomerism in Co-M (M = Cu, Ag, Au) Carbonyl Clusters: Synthesis, Structures and Computational Investigation
title_full_unstemmed Polymerization Isomerism in Co-M (M = Cu, Ag, Au) Carbonyl Clusters: Synthesis, Structures and Computational Investigation
title_short Polymerization Isomerism in Co-M (M = Cu, Ag, Au) Carbonyl Clusters: Synthesis, Structures and Computational Investigation
title_sort polymerization isomerism in co-m (m = cu, ag, au) carbonyl clusters: synthesis, structures and computational investigation
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7998641/
https://www.ncbi.nlm.nih.gov/pubmed/33799629
http://dx.doi.org/10.3390/molecules26061529
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