Zirconium and Hafnium Hydrazinediido Half-Sandwich Complexes: Synthesis and Reactivity

The hydrazinediido complexes [Cp*M(NxylN)(NNPh2)(dmap)] (M = Zr, 3a; M = Hf, 3b; NxylN = 2-(N-xylylamino)pyrrolinate) have been synthesized, and their reactivity has been investigated. Both complexes were prepared from [Cp*M(NxylN)Cl2] (1a,b) and [Cp*M(NxylN)(NHNPh2)Cl] (2a,b), respectively, as prec...

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Published in:Organometallics 2014-04, Vol.33 (7), p.1726-1739
Main Authors: Schweizer, Peter D, Wadepohl, Hubert, Gade, Lutz H
Format: Article
Language:English
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Summary:The hydrazinediido complexes [Cp*M(NxylN)(NNPh2)(dmap)] (M = Zr, 3a; M = Hf, 3b; NxylN = 2-(N-xylylamino)pyrrolinate) have been synthesized, and their reactivity has been investigated. Both complexes were prepared from [Cp*M(NxylN)Cl2] (1a,b) and [Cp*M(NxylN)(NHNPh2)Cl] (2a,b), respectively, as precursors. While 3a was obtained by dehydrohalogenation of 2a using LiHMDS in the presence of dmap, reaction of 2b with LiHMDS initially afforded a mixture of [Cp*Hf(NxylN)(NHNPh2)2] (6) and [Cp*Hf(NxylN)(NNPh2)LiHMDS] (4), which was thermolyzed subsequently in the presence of dmap to yield 3b. [Cp*Zr(NxylN)(NNPh2)(dmap)] (3a) reacted with diisopropylcarbodiimide, giving the rearranged [2 + 2] cycloaddition product [Cp*Zr(NXylN){κ2-NiPrC(NNPh2)NiPr}] (7) and the six-membered zirconacycle [Cp*Zr(NXylN){κ2-N(NPh2)C(NiPr)NiPrC(NiPr)NiPr}] (8a). With N-phenylbenzimine the cycloaddition product [Cp*Zr(NXylN){κ2-N(NPh2)CHPhNPh}] (9) was isolated, and upon reaction with diphenylacetylene the seven-membered zirconacycle [Cp*Zr(NXylN){κ2-N(Ph)-o-phenylene-C(Ph)C(Ph)NH}] (10) was obtained. Reaction of the previously synthesized compound [Zr(N2 TBSNpy)(NNPh2)py] (11) with i PrNCN i Pr and with PhCHNPh gave the four-membered zirconacycles [Zr(N2 TBSNpy){κ2-N(NPh2)C(NiPr)NiPr}] (12) and [Zr(N2 TBSNpy){κ2-N(NPh2)CHPhNPh}] (13), respectively.
ISSN:0276-7333
1520-6041
DOI:10.1021/om500087s