Pitfalls and limitations in Group 6 triamidophosphane chemistry

• Verfasst von: Sietzen, Malte [VerfasserIn]
• Verfasst von: Batke, Sonja [VerfasserIn]
• Verfasst von: Merz, Lukas [VerfasserIn]
• Verfasst von: Wadepohl, Hubert [VerfasserIn]
• Verfasst von: Ballmann, Joachim [VerfasserIn]
• Titel: Pitfalls and limitations in Group 6 triamidophosphane chemistry
• Titelzusatz: cage-closure restrictions in square-pyramidal nitrido complexes and degradation via spiro-[4.4]-[lambda]5-amidophosphorane formation
• Verf.angabe: Malte Sietzen, Sonja Batke, Lukas Merz, Hubert Wadepohl, and Joachim Ballmann
• Jahr: 2017
• Umfang: 9 S.
• Fussnoten: Im Zusatz zum Titel ist „5“ nach [lambda] hochgestellt ; Gesehen am 29.08.2018
• Titel Quelle: Enthalten in: European journal of inorganic chemistry
• Ort Quelle: Weinheim : Wiley-VCH, 1998
• Jahr Quelle: 2017
• Band/Heft Quelle: (2017), 46, Seite 5442-5450
• ISSN Quelle: 1099-0682
• DOI: doi:10.1002/ejic.201701023
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: Molybdenum
• Sach-SW: N
• Sach-SW: Nitrido complexes
• Sach-SW: P ligands
• Sach-SW: Spiro compounds
• Sach-SW: Tripodal ligands
• K10plus-PPN: 1580486622

Abstract

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.