Controlling concatenation in germanium(I) chemistry through hemilability
We present a novel approach for constructing chains of Group 14 metal atoms linked by unsupported metal–metal bonds that exploits hemilabile ligands to generate unsaturated metal sites. The formation/nature of catenated species (oligo-dimetallynes) can be controlled by the use of (acidic/basic) “pro...
| প্রধান লেখক: | , , , , , |
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| বিন্যাস: | Journal article |
| ভাষা: | English |
| প্রকাশিত: |
Wiley
2021
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| _version_ | 1826288050084249600 |
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| author | Caise, A Griffin, LP Heilmann, A McManus, C Campos, J Aldridge, S |
| author_facet | Caise, A Griffin, LP Heilmann, A McManus, C Campos, J Aldridge, S |
| author_sort | Caise, A |
| collection | OXFORD |
| description | We present a novel approach for constructing chains of Group 14 metal atoms linked by unsupported metal–metal bonds that exploits hemilabile ligands to generate unsaturated metal sites. The formation/nature of catenated species (oligo-dimetallynes) can be controlled by the use of (acidic/basic) “protecting groups” and through variation of the ligand scaffold. Reduction of ArNiPr2GeCl (ArNiPr2=2,6-(iPr2NCH2)2C6H3)—featuring hemilabile NiPr2 donors—yields (ArNiPr2Ge)4 (2), which contains a tetrameric Ge4 chain. 2 represents a novel type of a linear homo-catenated GeI compound featuring unsupported E−E bonds. Trapping experiments reveal that a key structural component is the central two-way Ge=Ge donor-acceptor bond: reactions with IMe4 and W(CO)5(NMe3) give the base- or acid-stabilized digermynes (ArNiPr2Ge(IMe4))2 (4) and (ArNiPr2Ge{W(CO)5})2 (5), respectively. The use of smaller N-donors leads to stronger Ge-N interactions and quenching of catenation behaviour: reduction of ArNEt2GeCl gives the digermyne (ArNEt2Ge)2, while the unsymmetrical system ArNEt2GeGeArNiPr2 dimerizes to give tetranuclear (ArNEt2GeGeArNiPr2)2 through aggregation at the NiPr2-ligated GeI centres. |
| first_indexed | 2024-03-07T02:07:52Z |
| format | Journal article |
| id | oxford-uuid:9f99ccac-830b-4fac-94d5-eed29b2ecf0d |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T02:07:52Z |
| publishDate | 2021 |
| publisher | Wiley |
| record_format | dspace |
| spelling | oxford-uuid:9f99ccac-830b-4fac-94d5-eed29b2ecf0d2022-03-27T00:59:16ZControlling concatenation in germanium(I) chemistry through hemilabilityJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:9f99ccac-830b-4fac-94d5-eed29b2ecf0dEnglishSymplectic ElementsWiley2021Caise, AGriffin, LPHeilmann, AMcManus, CCampos, JAldridge, SWe present a novel approach for constructing chains of Group 14 metal atoms linked by unsupported metal–metal bonds that exploits hemilabile ligands to generate unsaturated metal sites. The formation/nature of catenated species (oligo-dimetallynes) can be controlled by the use of (acidic/basic) “protecting groups” and through variation of the ligand scaffold. Reduction of ArNiPr2GeCl (ArNiPr2=2,6-(iPr2NCH2)2C6H3)—featuring hemilabile NiPr2 donors—yields (ArNiPr2Ge)4 (2), which contains a tetrameric Ge4 chain. 2 represents a novel type of a linear homo-catenated GeI compound featuring unsupported E−E bonds. Trapping experiments reveal that a key structural component is the central two-way Ge=Ge donor-acceptor bond: reactions with IMe4 and W(CO)5(NMe3) give the base- or acid-stabilized digermynes (ArNiPr2Ge(IMe4))2 (4) and (ArNiPr2Ge{W(CO)5})2 (5), respectively. The use of smaller N-donors leads to stronger Ge-N interactions and quenching of catenation behaviour: reduction of ArNEt2GeCl gives the digermyne (ArNEt2Ge)2, while the unsymmetrical system ArNEt2GeGeArNiPr2 dimerizes to give tetranuclear (ArNEt2GeGeArNiPr2)2 through aggregation at the NiPr2-ligated GeI centres. |
| spellingShingle | Caise, A Griffin, LP Heilmann, A McManus, C Campos, J Aldridge, S Controlling concatenation in germanium(I) chemistry through hemilability |
| title | Controlling concatenation in germanium(I) chemistry through hemilability |
| title_full | Controlling concatenation in germanium(I) chemistry through hemilability |
| title_fullStr | Controlling concatenation in germanium(I) chemistry through hemilability |
| title_full_unstemmed | Controlling concatenation in germanium(I) chemistry through hemilability |
| title_short | Controlling concatenation in germanium(I) chemistry through hemilability |
| title_sort | controlling concatenation in germanium i chemistry through hemilability |
| work_keys_str_mv | AT caisea controllingconcatenationingermaniumichemistrythroughhemilability AT griffinlp controllingconcatenationingermaniumichemistrythroughhemilability AT heilmanna controllingconcatenationingermaniumichemistrythroughhemilability AT mcmanusc controllingconcatenationingermaniumichemistrythroughhemilability AT camposj controllingconcatenationingermaniumichemistrythroughhemilability AT aldridges controllingconcatenationingermaniumichemistrythroughhemilability |