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(2 + 2) Cycloaddition products of zirconium and hafnium hydrazinediides with allenes and heteroallenes and their thermally induced rearrangements

Reactions of the hydrazinediido complexes [M(N2TBSNpy)(NNPh2)(py)] (M = Zr (1a), Hf (1b)) with (hetero)allenes result in a variety of [2 + 2] cycloaddition products of the general type [M(N2TBSNpy)(κ2N,E-(E(═E′R)NNPh2)(py)] (E = CH2, S; E′ = CH, N; R = alkyl, aryl). The reaction of [Zr(N2TBSNpy)(NNP...

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Bibliographische Detailangaben
Hauptverfasser: Gehrmann, Thorsten (VerfasserIn) , Plundrich, Gudrun (VerfasserIn) , Wadepohl, Hubert (VerfasserIn) , Gade, Lutz H. (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: April 3, 2012
In: Organometallics
Year: 2012, Jahrgang: 31, Heft: 8, Pages: 3346-3354
ISSN:1520-6041
DOI:10.1021/om300143h
Online-Zugang:Verlag, Volltext: http://dx.doi.org/10.1021/om300143h
Verlag, Volltext: https://doi.org/10.1021/om300143h
Volltext
Verfasserangaben:Thorsten Gehrmann, Gudrun T. Plundrich, Hubert Wadepohl, and Lutz H. Gade
Beschreibung
Zusammenfassung:Reactions of the hydrazinediido complexes [M(N2TBSNpy)(NNPh2)(py)] (M = Zr (1a), Hf (1b)) with (hetero)allenes result in a variety of [2 + 2] cycloaddition products of the general type [M(N2TBSNpy)(κ2N,E-(E(═E′R)NNPh2)(py)] (E = CH2, S; E′ = CH, N; R = alkyl, aryl). The reaction of [Zr(N2TBSNpy)(NNPh2)(py)] (1a) with 1 molar equiv of phenyl or mesityl isothiocyanate at room temperature yields [Zr(N2TBSNpy)(κ2N,S-SC(═NAr)NNPh2)(py)] (Ar = phenyl (2a), mesityl (2b)). Reacting the hydrazinediides [M(N2TBSNpy)(NNPh2)(py)] (M = Zr (1a), Hf (1b)) with allenes results in the formation of the metallaazacyclobutanes [M(N2TBSNpy)(κ2N,C-N(NPh2)CH2C═CH(R))(py)] (M = Zr, R = Ph (4a), cyclohexyl (5a), methyl (6); M = Hf, R = phenyl (4b), cyclohexyl (5b)). Subsequent heating of the cycloaddition products revealed different reactivity patterns: the complex [Zr(N2TBSNpy)(κ2N,S-SC(═NAr)NNPh2)(py)] (2a) forms the isomerization product [Zr(N2TBSNpy)(κ2N,S-SC(═NNPh2))NPh] (3), retaining the N-N bond of the hydrazide. In contrast, the metallacyclobutanes 4a,b and 5a,b show a tendency toward N-N bond cleavage, resulting in the formation of the C-N- and C-C-coupled product complexes [M(κ4N,N,N,N-N2TBSNpyNC(Me)═CHCy)(NPh2)] (M = Zr (7a), Hf (7b)), [Zr(N2TBSNpy)(κ2N,C-(Ph)NC6H4C(Me)═C(Ph)NH)] (8) and [Zr(κ4N,N,N,N-N2TBSNpyNC(Me)=CHPh)(NPh2)] (9).
Beschreibung:Gesehen am 17.05.2018
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Beschreibung:Online Resource
ISSN:1520-6041
DOI:10.1021/om300143h

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