Pitfalls and limitations in Group 6 triamidophosphane chemistry: cage-closure restrictions in square-pyramidal nitrido complexes and degradation via spiro-[4.4]-[lambda]5-amidophosphorane formation
The benzylene-linked triaminophosphanes P(C6H4-o-CH2NHXyl)3 ([A]H3) and P(CH2C6H4-o-NHPh)3 ([B]H3) react with (Me2N)3Mo≡N to afford the square-pyramidal nitrido complexes 1 and 2, each comprising one residual dimethylamido moiety and one uncoordinated ligand sidearm. Only the [A]-coordinated complex...
Saved in:
| Main Authors: | , , , , |
|---|---|
| Format: | Article (Journal) |
| Language: | English |
| Published: |
2017
|
| In: |
European journal of inorganic chemistry
Year: 2017, Issue: 46, Pages: 5442-5450 |
| ISSN: | 1099-0682 |
| DOI: | 10.1002/ejic.201701023 |
| Online Access: | Verlag, Volltext: http://dx.doi.org/10.1002/ejic.201701023 Verlag, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/ejic.201701023 
|
| Author Notes: | Malte Sietzen, Sonja Batke, Lukas Merz, Hubert Wadepohl, and Joachim Ballmann |
| Summary: | The benzylene-linked triaminophosphanes P(C6H4-o-CH2NHXyl)3 ([A]H3) and P(CH2C6H4-o-NHPh)3 ([B]H3) react with (Me2N)3Mo≡N to afford the square-pyramidal nitrido complexes 1 and 2, each comprising one residual dimethylamido moiety and one uncoordinated ligand sidearm. Only the [A]-coordinated complex 1 was found to eliminate the remaining dimethylamido ligand on heating. Instead of the closed-cage molybdenum(VI) nitrido complex [A]Mo≡N, cyclometalated molybdaziridine 3 was isolated, as the syn alignment of the uncoordinated sidearm and nitrido ligand in 1 inhibits a productive cage-closure reaction. By using [NPN]-coordinated model complexes, analogous syn arrangements were found not only for molybdenum, but also for the related tungsten nitrido complexes and the group 5 imides. Attempts to access the closed-cage MoVI nitrido comlex [A]Mo≡N by transmetalation between [A]Sn(nBu) (9) and (tBuO)3Mo≡N led to the formation of spiro-[4.4]-λ5-amidophosphorane 10. These results contrast with the findings made for azatranes and methylene-linked exo-P-configured triamidophosphane complexes. |
|---|---|
| Item Description: | Im Zusatz zum Titel ist „5“ nach [lambda] hochgestellt Gesehen am 29.08.2018 |
| Physical Description: | Online Resource |
| ISSN: | 1099-0682 |
| DOI: | 10.1002/ejic.201701023 |