Facile Access to NaOC≡As and Its Use as an Arsenic Source To Form Germylidenylarsinidene Complexes
| Autor: | Matthias Driess, Arseni Kostenko, Hansjörg Grützmacher, Ernesto Ballestero-Martínez, Mark Bispinghoff, Yves Grossheim, Shenglai Yao, Stefan Schutte |
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| Rok vydání: | 2017 |
| Předmět: |
010405 organic chemistry
Ligand chemistry.chemical_element General Medicine General Chemistry 010402 general chemistry Ring (chemistry) Photochemistry 01 natural sciences Medicinal chemistry Catalysis 0104 chemical sciences chemistry.chemical_compound Arsine chemistry Yield (chemistry) Atom Carbene Arsenic |
| Zdroj: | Angewandte Chemie International Edition. 56:7465-7469 |
| ISSN: | 1433-7851 |
| DOI: | 10.1002/anie.201703731 |
| Popis: | A facile, one-pot synthesis of [Na(OCAs)(dioxane)x] (x = 2.3 - 3.3) in 78% yield is reported through the reaction of arsine gas with dimethylcarbonate in the presence of NaOtBu and 1,4-dioxane. It has been employed for the synthesis of the first arsaketenyl-functionalized germylene [LGeAsCO] (2, L = CH[CMeNDipp]2, Dipp = 2,6-iPr2C6H3) from the reaction with LGeCl 1. If exposed to daylight, 2 undergoes CO elimination to form the 1,3-digerma-2,4-diarsacyclobutadiene [L2Ge2As2] 3 which contains a symmetric Ge2As2 ring with ylide-like Ge=As bonds. Remarkably, the CO ligand at the arsenic center of 2 can be exchanged with PPh3 or an N-heterocyclic carbene donor to afford the novel germylidenylarsinidene complexes [LGe-AsPPh3] 4 and [LGe-As(NHC)] 5, respectively, demonstrating transition metal-like ligand substitution at the arsinidene-like As atom. The formation of 2-5 and their electronic structures have been studied by DFT calculations. |
| Databáze: | OpenAIRE |
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