| Title: |
Facile Access to NaOC≡As and Its Use as an Arsenic Source To Form Germylidenylarsinidene Complexes |
| Authors: |
Yao, Shenglai; Grossheim, Yves; Kostenko, Arseni; Ballestero‐Martínez, Ernesto; Schutte, Stefan; Bispinghoff, Mark; Grützmacher, Hansjörg; Driess, Matthias |
| Contributors: |
Deutsche Forschungsgemeinschaft |
| Source: |
Angewandte Chemie ; volume 129, issue 26, page 7573-7577 ; ISSN 0044-8249 1521-3757 |
| Publisher Information: |
Wiley |
| Publication Year: |
2017 |
| Collection: |
Wiley Online Library (Open Access Articles via Crossref) |
| Description: |
A facile, one‐pot synthesis of [Na(OC≡As)(dioxane) x ] ( x =2.3–3.3) in 78 % yield is reported through the reaction of arsine gas with dimethylcarbonate in the presence of NaO t Bu and 1,4‐dioxane. It has been employed for the synthesis of the first arsaketenyl‐functionalized germylene [LGeAsCO] ( 2 , L=CH[CMeN(Dipp)] 2 ; Dipp=2,6‐ i Pr 2 C 6 H 3 ) from the reaction with LGeCl ( 1 ). Upon exposure to ambient light, 2 undergoes CO elimination to form the 1,3‐digerma‐2,4‐diarsacyclobutadiene [L 2 Ge 2 As 2 ] ( 3 ), which contains a symmetric Ge 2 As 2 ring with ylide‐like Ge=As bonds. Remarkably, the CO ligand located at the arsenic center of 2 can be exchanged with PPh 3 or an N‐heterocyclic carbene i Pr NHC donor ( i Pr NHC=1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene) to afford the novel germylidenylarsinidene complexes [LGe‐AsPPh 3 ] ( 4 ) and [LGe‐As( i Pr 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. |
| Document Type: |
article in journal/newspaper |
| Language: |
English |
| DOI: |
10.1002/ange.201703731 |
| Availability: |
https://doi.org/10.1002/ange.201703731; https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fange.201703731; https://onlinelibrary.wiley.com/doi/pdf/10.1002/ange.201703731 |
| Rights: |
http://onlinelibrary.wiley.com/termsAndConditions#vor |
| Accession Number: |
edsbas.A775C525 |
| Database: |
BASE |