Synthesis, Characterization, and Catalytic Exploration of Mononuclear Mo(VI) Dioxido Complexes of (<i>Z</i>)-1-<i>R</i>-2-(4′,4′-Dimethyl-2′-oxazolin-2′-yl)-eth-1-en-1-ates
The coordination chemistry of the title ligands with Mo metal centers was investigated. Thus, the synthesis and characterization (NMR, X-ray diffraction) of four mononuclear formally Mo(6+) complexes of (<i>Z</i>)-1-<i>R</i>-2-(4′,4′-dimethyl-2′-oxazolin-2′-yl)-eth-1-en-1-ate...
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MDPI AG
2022-02-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/4/1309 |
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| author | Anna Petrov Jeanette A. Adjei Alan J. Lough R. Stephen Wylie Robert A. Gossage |
| author_facet | Anna Petrov Jeanette A. Adjei Alan J. Lough R. Stephen Wylie Robert A. Gossage |
| author_sort | Anna Petrov |
| collection | DOAJ |
| description | The coordination chemistry of the title ligands with Mo metal centers was investigated. Thus, the synthesis and characterization (NMR, X-ray diffraction) of four mononuclear formally Mo(6+) complexes of (<i>Z</i>)-1-<i>R</i>-2-(4′,4′-dimethyl-2′-oxazolin-2′-yl)-eth-1-en-1-ates (L: R = –Ph, –Ph-<i>p</i>-NO<sub>2</sub>, –Ph-<i>p</i>-OMe and –<i>t</i>-Bu), derived from the part enols (LH), is described. The resulting air-stable MoO<sub>2</sub>L<sub>2</sub> complexes (<b>1</b>–<b>4</b>) exist, as shown by single-crystal X-ray diffraction experiments, in the <i>cis</i>-dioxido-<i>trans(N)</i>-κ<sup>2</sup>-<i>N</i>,<i>O</i>-L conformation in the solid state for all four examples. This situation was further probed using semi-empirical PM6(tm) calculations. Complexes <b>1</b>–<b>4</b> represent the first Mo complexes of this ligand class and, indeed, of Group 6 metals in general. Structural and spectroscopic comparisons were made between these and related Mo(6+) compounds. Complex <b>1</b> (R = –Ph) was studied for its ability to selectively catalyze the production of <i>poly</i>-norbornene from the monomer in the presence of MAO. This, unfortunately, only resulted in the synthesis of insoluble, presumably highly cross-linked, polymeric and/or oligomeric materials. However, complexes <b>1</b>–<b>4</b> were demonstrated to be highly effective for catalyzing benzoin to benzil conversion using DMSO as the <i>O</i>-transfer agent. This catalysis work is likewise put into perspective with respect to analogous Mo(6+) complexes. |
| first_indexed | 2024-03-09T21:20:34Z |
| format | Article |
| id | doaj.art-2b4881ab66b9473ea1cbb3d16392ee0f |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T21:20:34Z |
| publishDate | 2022-02-01 |
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| spelling | doaj.art-2b4881ab66b9473ea1cbb3d16392ee0f2023-11-23T21:22:08ZengMDPI AGMolecules1420-30492022-02-01274130910.3390/molecules27041309Synthesis, Characterization, and Catalytic Exploration of Mononuclear Mo(VI) Dioxido Complexes of (<i>Z</i>)-1-<i>R</i>-2-(4′,4′-Dimethyl-2′-oxazolin-2′-yl)-eth-1-en-1-atesAnna Petrov0Jeanette A. Adjei1Alan J. Lough2R. Stephen Wylie3Robert A. Gossage4Department of Chemistry & Biology, Ryerson University, 350 Victoria Street, Toronto, ON M5B 2K3, CanadaDepartment of Chemistry & Biology, Ryerson University, 350 Victoria Street, Toronto, ON M5B 2K3, CanadaX-ray Crystallography Laboratory, University of Toronto, Toronto, ON M5S 3H6, CanadaDepartment of Chemistry & Biology, Ryerson University, 350 Victoria Street, Toronto, ON M5B 2K3, CanadaDepartment of Chemistry & Biology, Ryerson University, 350 Victoria Street, Toronto, ON M5B 2K3, CanadaThe coordination chemistry of the title ligands with Mo metal centers was investigated. Thus, the synthesis and characterization (NMR, X-ray diffraction) of four mononuclear formally Mo(6+) complexes of (<i>Z</i>)-1-<i>R</i>-2-(4′,4′-dimethyl-2′-oxazolin-2′-yl)-eth-1-en-1-ates (L: R = –Ph, –Ph-<i>p</i>-NO<sub>2</sub>, –Ph-<i>p</i>-OMe and –<i>t</i>-Bu), derived from the part enols (LH), is described. The resulting air-stable MoO<sub>2</sub>L<sub>2</sub> complexes (<b>1</b>–<b>4</b>) exist, as shown by single-crystal X-ray diffraction experiments, in the <i>cis</i>-dioxido-<i>trans(N)</i>-κ<sup>2</sup>-<i>N</i>,<i>O</i>-L conformation in the solid state for all four examples. This situation was further probed using semi-empirical PM6(tm) calculations. Complexes <b>1</b>–<b>4</b> represent the first Mo complexes of this ligand class and, indeed, of Group 6 metals in general. Structural and spectroscopic comparisons were made between these and related Mo(6+) compounds. Complex <b>1</b> (R = –Ph) was studied for its ability to selectively catalyze the production of <i>poly</i>-norbornene from the monomer in the presence of MAO. This, unfortunately, only resulted in the synthesis of insoluble, presumably highly cross-linked, polymeric and/or oligomeric materials. However, complexes <b>1</b>–<b>4</b> were demonstrated to be highly effective for catalyzing benzoin to benzil conversion using DMSO as the <i>O</i>-transfer agent. This catalysis work is likewise put into perspective with respect to analogous Mo(6+) complexes.https://www.mdpi.com/1420-3049/27/4/1309oxazoline-enolate chelatesmolybdenum(6+) oxide complexesX-ray structure determinationbenzoin oxidationsemi-empirical PM6(tm) calculations |
| spellingShingle | Anna Petrov Jeanette A. Adjei Alan J. Lough R. Stephen Wylie Robert A. Gossage Synthesis, Characterization, and Catalytic Exploration of Mononuclear Mo(VI) Dioxido Complexes of (<i>Z</i>)-1-<i>R</i>-2-(4′,4′-Dimethyl-2′-oxazolin-2′-yl)-eth-1-en-1-ates Molecules oxazoline-enolate chelates molybdenum(6+) oxide complexes X-ray structure determination benzoin oxidation semi-empirical PM6(tm) calculations |
| title | Synthesis, Characterization, and Catalytic Exploration of Mononuclear Mo(VI) Dioxido Complexes of (<i>Z</i>)-1-<i>R</i>-2-(4′,4′-Dimethyl-2′-oxazolin-2′-yl)-eth-1-en-1-ates |
| title_full | Synthesis, Characterization, and Catalytic Exploration of Mononuclear Mo(VI) Dioxido Complexes of (<i>Z</i>)-1-<i>R</i>-2-(4′,4′-Dimethyl-2′-oxazolin-2′-yl)-eth-1-en-1-ates |
| title_fullStr | Synthesis, Characterization, and Catalytic Exploration of Mononuclear Mo(VI) Dioxido Complexes of (<i>Z</i>)-1-<i>R</i>-2-(4′,4′-Dimethyl-2′-oxazolin-2′-yl)-eth-1-en-1-ates |
| title_full_unstemmed | Synthesis, Characterization, and Catalytic Exploration of Mononuclear Mo(VI) Dioxido Complexes of (<i>Z</i>)-1-<i>R</i>-2-(4′,4′-Dimethyl-2′-oxazolin-2′-yl)-eth-1-en-1-ates |
| title_short | Synthesis, Characterization, and Catalytic Exploration of Mononuclear Mo(VI) Dioxido Complexes of (<i>Z</i>)-1-<i>R</i>-2-(4′,4′-Dimethyl-2′-oxazolin-2′-yl)-eth-1-en-1-ates |
| title_sort | synthesis characterization and catalytic exploration of mononuclear mo vi dioxido complexes of i z i 1 i r i 2 4 4 dimethyl 2 oxazolin 2 yl eth 1 en 1 ates |
| topic | oxazoline-enolate chelates molybdenum(6+) oxide complexes X-ray structure determination benzoin oxidation semi-empirical PM6(tm) calculations |
| url | https://www.mdpi.com/1420-3049/27/4/1309 |
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