Isolation of the Metalated Ylides [Ph3P−C−CN]M (M=Li, Na, K): Influence of the Metal Ion on the Structure and Bonding Situation
Please always quote using this URN: urn:nbn:de:bvb:20-opus-235445
- The isolation and structural characterization of the cyanido-substituted metalated ylides [Ph3P−C−CN]M (1-M; M=Li, Na, K) are reported with lithium, sodium, and potassium as metal cations. In the solid-state, most different aggregates could be determined depending on the metal and additional Lewis bases. The crown-ether complexes of sodium (1-Na) and potassium (1-K) exhibited different structures, with sodium preferring coordination to the nitrogen end, whereas potassium binds in an unusual η2-coordination mode to the two central carbon atoms.The isolation and structural characterization of the cyanido-substituted metalated ylides [Ph3P−C−CN]M (1-M; M=Li, Na, K) are reported with lithium, sodium, and potassium as metal cations. In the solid-state, most different aggregates could be determined depending on the metal and additional Lewis bases. The crown-ether complexes of sodium (1-Na) and potassium (1-K) exhibited different structures, with sodium preferring coordination to the nitrogen end, whereas potassium binds in an unusual η2-coordination mode to the two central carbon atoms. The formation of the yldiide was accompanied by structural changes leading to shorter C−C and longer C−N bonds. This could be attributed to the delocalization of the free electron pairs at the carbon atom into the antibonding orbitals of the CN moiety, which was confirmed by IR spectroscopy and computational studies. Detailed density functional theory calculations show that the changes in the structure and the bonding situation were most pronounced in the lithium compounds due to the higher covalency.…
Author: | Christopher Schwarz, Lennart T. Scharf, Thorsten Scherpf, Julia Weismann, Viktoria H. Gessner |
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URN: | urn:nbn:de:bvb:20-opus-235445 |
Document Type: | Journal article |
Faculties: | Fakultät für Chemie und Pharmazie / Institut für Anorganische Chemie |
Language: | English |
Parent Title (English): | Chemistry – A European Journal |
Year of Completion: | 2019 |
Volume: | 25 |
Pagenumber: | 2793-2802 |
Source: | Chemistry – A European Journal (2019) 25:2793-2802. https://doi.org/10.1002/chem.201805421 |
DOI: | https://doi.org/10.1002/chem.201805421 |
Dewey Decimal Classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften |
Tag: | alkali metals; bond theory; lithium; solid-state structures; structure elucidation; ylides |
Release Date: | 2024/08/22 |
EU-Project number / Contract (GA) number: | 677749 |
OpenAIRE: | OpenAIRE |
Licence (German): | CC BY: Creative-Commons-Lizenz: Namensnennung 4.0 International |