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Stepwise Functionalization of N2 at Mo: Nitrido to Imido to Amido – Factors Favoring Amine Elimination from the Amido Complex.
- Source :
- European Journal of Inorganic Chemistry; 4/30/2020, Vol. 2020 Issue 15/16, p1499-1505, 7p
- Publication Year :
- 2020
-
Abstract
- Functionalization of nitrido complex [(PPhP2Cy)Mo(N)(I)] by a bis‐silane in concentrated medium generates the hydrido‐imido complex [(PPhP2Cy)Mo(H)(=NSiMe2CH2CH2SiMe2H)(I)]. Abstraction of the iodide by thallium salt TlX (X = PF6, OTf) results in a second N–Si bond formation and forms the bis‐hydride amide complex [(PPhP2Cy)Mo(H)2(NSiMe2CH2CH2SiMe2)]+. An alternative synthesis relies on the abstraction of the iodide from the nitride complex [(PPhP2Cy)Mo(N)(I)] to generate the corresponding cationic complex [(PPhP2Cy)Mo(N)]+ followed by addition of the bis‐silane. Addition of PMe3 to the [(PPhP2Cy)Mo(H)2(NSiMe2CH2CH2SiMe2)]+ complex liberates the silylamine and forms the Mo(II) cationic complex [(PPhP2Cy)Mo(H)(PMe3)]+. DFT calculations rationalizing the observed reactivity are presented. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 14341948
- Volume :
- 2020
- Issue :
- 15/16
- Database :
- Complementary Index
- Journal :
- European Journal of Inorganic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 142867774
- Full Text :
- https://doi.org/10.1002/ejic.201901295