| Online-Ressource |
Verfasst von: | Gehrmann, Thorsten [VerfasserIn]  |
| Lloret Fillol, Julio [VerfasserIn]  |
| Herrmann, Heike [VerfasserIn]  |
| Wadepohl, Hubert [VerfasserIn]  |
| Gade, Lutz H. [VerfasserIn]  |
Titel: | Zirconium hydrazides as metallanitrene synthons |
Titelzusatz: | release of molecular N2 from a hydrazinediido complex induced by oxidative N-N bond cleavage |
Verf.angabe: | Thorsten Gehrmann, Julio Lloret-Fillol, Heike Herrmann, Hubert Wadepohl, and Lutz H. Gade |
E-Jahr: | 2013 |
Jahr: | July 8, 2013 |
Umfang: | 13 S. |
Fussnoten: | Gesehen am 29.01.2020 ; Im Titelzusatz ist die Zahl "2" tiefgestellt |
Titel Quelle: | Enthalten in: Organometallics |
Ort Quelle: | Washington, DC : ACS Publ., 1982 |
Jahr Quelle: | 2013 |
Band/Heft Quelle: | 32(2013), 14, Seite 3877-3889 |
ISSN Quelle: | 1520-6041 |
Abstract: | The N-N bond in the zirconium hydrazinediido(2−) complex [Zr(N2TBSNpy)(NNPh2)(py)] (1) is readily cleaved by one-electron oxidation. Reacting [Zr(N2TBSNpy)(NNPh2)(py)] (1) with 0.5 molar equiv of iodine led to the release of molecular N2 and yielded the mixed diphenylamido/iodo complex [Zr(N2TBSNpyNPh2)(I)] (2). Exposure of hydrazinediide 1 to an excess of iodine resulted in further oxidation of the diphenylamido ligand, yielding the diiodo complex 3 and tetraphenylhydrazine. Similar reactivity was observed in the reaction of 1 with diphenyl diselenide and diaryl disulfides, which reacted to give the corresponding diphenylamido/arylchalcogenido complexes [Zr(N2TBSNpyNPh2)(SePh)] (4a) and [Zr(N2TBSNpy)(NPh2)(SAr)] (Ar = Ph (4b), C6F5 (4c)) along with N2. The reactions were also carried out on an NMR scale with a 15Nα-labeled hydrazido complex (1-15N). In all cases a single 15N NMR resonance at 310.16 ppm, assigned to 15N2, indicated the formation of dinitrogen from the Nα atom in the hydrazide. A crossover labeling experiment employing a 1:1 mixture of 1 and 15Nα-labeled 1-15N revealed that the isotope distribution is, as expected, statistical 1:2:1 (14N2: 14/15N2: 15N2), which is consistent with a reaction pathway involving a dinuclear intermediate in the dinitrogen-forming step. Complex 1 reacted with N2O to give a mixture of two compounds, the bis(diphenylamido) complex 6 and the doubly bridged μ-oxo complex 7. In contrast, reaction of 1 with 1 molar equiv of pyridinium N-oxide only gave the doubly bridged μ-oxo complex 7 along with 2,2′-bipyridine and diphenylamine. |
DOI: | doi:10.1021/om400337g |
URL: | Bitte beachten Sie: Dies ist ein Bibliographieeintrag. Ein Volltextzugriff für Mitglieder der Universität besteht hier nur, falls für die entsprechende Zeitschrift/den entsprechenden Sammelband ein Abonnement besteht oder es sich um einen OpenAccess-Titel handelt.
Volltext: https://doi.org/10.1021/om400337g |
| DOI: https://doi.org/10.1021/om400337g |
Datenträger: | Online-Ressource |
Sprache: | eng |
K10plus-PPN: | 1745992510 |
Verknüpfungen: | → Zeitschrift |
Zirconium hydrazides as metallanitrene synthons / Gehrmann, Thorsten [VerfasserIn]; July 8, 2013 (Online-Ressource)