Synthesis and Characterization of New Cyclam-Based Zr(IV) Alkoxido Derivatives
In this study, new mono- and di-alkoxido zirconium(IV) complexes supported by tetradentate dianionic cyclam ligands were synthesized and characterized. These compounds were obtained by reaction of the parent Zr(IV) dichlorido species with one or two equivalents of the corresponding lithium alkoxido,...
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MDPI AG
2021-09-01
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| Series: | Reactions |
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| Online Access: | https://www.mdpi.com/2624-781X/2/3/21 |
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| author | Luis G. Alves Ana M. Martins |
| author_facet | Luis G. Alves Ana M. Martins |
| author_sort | Luis G. Alves |
| collection | DOAJ |
| description | In this study, new mono- and di-alkoxido zirconium(IV) complexes supported by tetradentate dianionic cyclam ligands were synthesized and characterized. These compounds were obtained by reaction of the parent Zr(IV) dichlorido species with one or two equivalents of the corresponding lithium alkoxido, whereas (<sup>3,5-Me2</sup>Bn<sub>2</sub>Cyclam)Zr(OPh)<sub>2</sub> was prepared by protonolysis of the orthometallated species (3,5-Me-C<sub>6</sub>H<sub>4</sub>CH<sub>2</sub>)<sub>2</sub>Cyclam)Zr with phenol. The solid-state molecular structures of (Bn<sub>2</sub>Cyclam)ZrCl(O<sup>t</sup>Bu) and (<sup>4-tBu</sup>Bn<sub>2</sub>Cyclam)Zr(O<sup>i</sup>Pr)<sub>2</sub> show a trigonal prismatic geometry around the metal centers. (Bn<sub>2</sub>Cyclam)Zr(SPh)(O<sup>t</sup>Bu) and (Bn<sub>2</sub>Cyclam)ZrMe(O<sup>i</sup>Pr) were prepared by reaction of (Bn<sub>2</sub>Cyclam)ZrCl(OR) (R = <sup>i</sup>Pr, <sup>t</sup>Bu) with one equivalent of LiSPh or MeMgCl, respectively. The reactions of (Bn<sub>2</sub>Cyclam)Zr(O<sup>i</sup>Pr)<sub>2</sub> and (<sup>4-tBu</sup>Bn<sub>2</sub>Cyclam)Zr(O<sup>i</sup>Pr)<sub>2</sub> with carbon dioxide suggested the formation of species that correspond to the addition of four CO<sub>2</sub> molecules. |
| first_indexed | 2024-03-10T07:16:42Z |
| format | Article |
| id | doaj.art-b2f27cc3265e48fbbd578378a53ca3c3 |
| institution | Directory Open Access Journal |
| issn | 2624-781X |
| language | English |
| last_indexed | 2024-03-10T07:16:42Z |
| publishDate | 2021-09-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Reactions |
| spelling | doaj.art-b2f27cc3265e48fbbd578378a53ca3c32023-11-22T15:02:35ZengMDPI AGReactions2624-781X2021-09-012332333210.3390/reactions2030021Synthesis and Characterization of New Cyclam-Based Zr(IV) Alkoxido DerivativesLuis G. Alves0Ana M. Martins1Centro de Química Estrutural, Associação do Instituto Superior Técnico Para a Investigação de Desenvolvimento, 1049-003 Lisboa, PortugalCentro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa, PortugalIn this study, new mono- and di-alkoxido zirconium(IV) complexes supported by tetradentate dianionic cyclam ligands were synthesized and characterized. These compounds were obtained by reaction of the parent Zr(IV) dichlorido species with one or two equivalents of the corresponding lithium alkoxido, whereas (<sup>3,5-Me2</sup>Bn<sub>2</sub>Cyclam)Zr(OPh)<sub>2</sub> was prepared by protonolysis of the orthometallated species (3,5-Me-C<sub>6</sub>H<sub>4</sub>CH<sub>2</sub>)<sub>2</sub>Cyclam)Zr with phenol. The solid-state molecular structures of (Bn<sub>2</sub>Cyclam)ZrCl(O<sup>t</sup>Bu) and (<sup>4-tBu</sup>Bn<sub>2</sub>Cyclam)Zr(O<sup>i</sup>Pr)<sub>2</sub> show a trigonal prismatic geometry around the metal centers. (Bn<sub>2</sub>Cyclam)Zr(SPh)(O<sup>t</sup>Bu) and (Bn<sub>2</sub>Cyclam)ZrMe(O<sup>i</sup>Pr) were prepared by reaction of (Bn<sub>2</sub>Cyclam)ZrCl(OR) (R = <sup>i</sup>Pr, <sup>t</sup>Bu) with one equivalent of LiSPh or MeMgCl, respectively. The reactions of (Bn<sub>2</sub>Cyclam)Zr(O<sup>i</sup>Pr)<sub>2</sub> and (<sup>4-tBu</sup>Bn<sub>2</sub>Cyclam)Zr(O<sup>i</sup>Pr)<sub>2</sub> with carbon dioxide suggested the formation of species that correspond to the addition of four CO<sub>2</sub> molecules.https://www.mdpi.com/2624-781X/2/3/21cyclamzirconiumalkoxidocomplexescarbon dioxide |
| spellingShingle | Luis G. Alves Ana M. Martins Synthesis and Characterization of New Cyclam-Based Zr(IV) Alkoxido Derivatives Reactions cyclam zirconium alkoxido complexes carbon dioxide |
| title | Synthesis and Characterization of New Cyclam-Based Zr(IV) Alkoxido Derivatives |
| title_full | Synthesis and Characterization of New Cyclam-Based Zr(IV) Alkoxido Derivatives |
| title_fullStr | Synthesis and Characterization of New Cyclam-Based Zr(IV) Alkoxido Derivatives |
| title_full_unstemmed | Synthesis and Characterization of New Cyclam-Based Zr(IV) Alkoxido Derivatives |
| title_short | Synthesis and Characterization of New Cyclam-Based Zr(IV) Alkoxido Derivatives |
| title_sort | synthesis and characterization of new cyclam based zr iv alkoxido derivatives |
| topic | cyclam zirconium alkoxido complexes carbon dioxide |
| url | https://www.mdpi.com/2624-781X/2/3/21 |
| work_keys_str_mv | AT luisgalves synthesisandcharacterizationofnewcyclambasedzrivalkoxidoderivatives AT anammartins synthesisandcharacterizationofnewcyclambasedzrivalkoxidoderivatives |