[2 + 2] Cycloaddition Products of Zirconium and Hafnium Hydrazinediides with Allenes and Heteroallenes and Their Thermally Induced Rearrangements

Gehrmann, Thorsten; Plundrich, Gudrun T.; Wadepohl, Hubert; Gade, Lutz H.

doi:10.1021/om300143h

Cited by 15 publications

(10 citation statements)

References 77 publications

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“…While the exocyclic CN bond length is consistent with a double bond (C(72)–N(57) 1.275 Å), both endocyclic CN bonds feature interatomic distances typical for single bonds (1.421 and 1.399 Å). These parameters are very similar to those of the corresponding titanium N -aminoguanidinato complex, and all other parameters are in good agreement with those of other previously reported cycloaddition products of 11 . , …”

Section: Resultssupporting

confidence: 89%

“…These parameters are very similar to those of the corresponding titanium N-aminoguanidinato complex, 16 and all other parameters are in good agreement with those of other previously reported cycloaddition products of 11. 27,30 Upon reaction of 11 with N-phenylbenzimine, formation of the zirconacycle 13 was observed (Scheme 5). The NMR spectra are consistent with the structure shown in Scheme 5.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Both the N(Ph)−CHPh and the N(NPh 2 )−CHPh bond lengths (1.460 and 1.495 Å) are typical for CN single bonds, and the other bond lengths and angles are in good agreement with those found in related cycloaddition products reported previously. 27,30…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Since we were not successful in obtaining single crystals of 8 and 9 that were suitable for an X-ray diffraction study, we chose to investigate the corresponding transformations with the zirconium complex 11 , which had been previously studied in our group (Scheme ). − ,− ,− …”

Section: Resultsmentioning

confidence: 99%

“…However, zirconium − and hafnium hydrazinediido complexes remain relatively scarce, despite the interesting and diverse reactive behavior found for some of them. − For stoichiometric reactions with disubstituted alkynes, formation of seven-membered zirconacycles via N–N-bond scission was observed, which provided the basis for a new catalytic indole synthesis. ,, This illustrates why further investigation into the chemistry of the heavier group 4 metals is desirable. To this end and in order to investigate the dependence of stoichiometric reactivity on both the ancillary ligand and metal, we have prepared new half-sandwich zirconium and hafnium complexes containing 2-( N -xylylamino)pyrrolinate (N xyl N) as a spectator ligand .…”

Section: Introductionmentioning

confidence: 99%

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

2014

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The hydrazinediido complexes [Cp*M(N xyl N)-(NNPh 2 )(dmap)] (M = Zr, 3a; M = Hf, 3b; N xyl N = 2-(Nxylylamino)pyrrolinate) have been synthesized, and their reactivity has been investigated. Both complexes were prepared from [Cp*M(N xyl N)Cl 2 ] (1a,b) and [Cp*M(N xyl N)-(NHNPh 2 )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

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Section: Resultssupporting

confidence: 89%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

2014

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Synthesis and Structural Characterization of a Lithium Alkynyl(hydrazinediido)zirconate and its Protonolysis to an Alkynylhydrazido(1–)zirconium Complex

Gehrmann

Wadepohl

Gade

2014

Zeitschrift anorg allge chemie

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Reaction of the hydrazinediido complex 1 with lithiated phenylacetylene selectively gave the lithium alkynyl(hydrazinediido)zirconate [(N 2 TBS N py )Zr{μ-NNPh 2 -1κN:2κN}{μ-PhCC-1κC:2κC}-Li(py)] (2), which reacted with one molar equivalent of TMEDA to give the corresponding Li-TMEDA derivative [(N 2 TBS N py )Zr{μ-NNPh 2 -1κN:2κN}{μ-PhCC-1κC:2κC}-Li(TMEDA)] (3). The details 40of the molecular structure of complex 3 were established by singlecrystal X-ray structure analysis. The lithium hydrazinediidozirconate 2 was treated with triethylammonium hydrochloride yielding the corresponding alkinylzirconium hydrazido(1-) complex 4 as a mixture of two diastereomers.Scheme 2. Protonation of the lithium hydrazinediidozirconate 2 with triethylammonium hydrochloride yielding the corresponding alkynylzirconium hydrazido(1-) complex 4a,b.

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Hafnium

Ishida¹,

Kawaguchi²

2021

Comprehensive Coordination Chemistry III

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[2 + 2] Cycloaddition Products of Zirconium and Hafnium Hydrazinediides with Allenes and Heteroallenes and Their Thermally Induced Rearrangements

Cited by 15 publications

References 77 publications

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

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

Synthesis and Structural Characterization of a Lithium Alkynyl(hydrazinediido)zirconate and its Protonolysis to an Alkynylhydrazido(1–)zirconium Complex

Hafnium

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