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Synthesis, characterization, and thermal rearrangement of zirconium tetraazadienyl and pentaazadienyl complexes

Reaction of the zirconium dichloro complex [Zr(N2TBSNpy)Cl2] (1) with 1 molar equiv of ArNHLi (Ar = Mes, DIPP) yielded the zirconium imido complexes [Zr(N2TBSNpy)(═NDIPP)(py)] (2; N2TBSNpy = [(2-C5H4N)C(CH3){CH2NSi(CH3)2tBu}2]2-, DIPP = 2,6-diisopropylphenyl) and [Zr(N2TBSNpy)(═NMes)(py)] (3; Mes =...

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Bibliographic Details
Main Authors: Gehrmann, Thorsten (Author) , Lloret Fillol, Julio (Author) , Wadepohl, Hubert (Author) , Gade, Lutz H. (Author)
Format: Article (Journal)
Language:English
Published: June 4, 2012
In: Organometallics
Year: 2012, Volume: 31, Issue: 12, Pages: 4504-4515
ISSN:1520-6041
DOI:10.1021/om300291b
Online Access:Verlag, Volltext: http://dx.doi.org/10.1021/om300291b
Verlag, Volltext: https://doi.org/10.1021/om300291b
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Author Notes:Thorsten Gehrmann, Julio Lloret Fillol, Hubert Wadepohl, and Lutz H. Gade
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Summary:Reaction of the zirconium dichloro complex [Zr(N2TBSNpy)Cl2] (1) with 1 molar equiv of ArNHLi (Ar = Mes, DIPP) yielded the zirconium imido complexes [Zr(N2TBSNpy)(═NDIPP)(py)] (2; N2TBSNpy = [(2-C5H4N)C(CH3){CH2NSi(CH3)2tBu}2]2-, DIPP = 2,6-diisopropylphenyl) and [Zr(N2TBSNpy)(═NMes)(py)] (3; Mes = mesityl). The imido complexes are converted to the tetraazadienido complexes [Zr(N2TBSNpy)(NDIPPN2NPh)] (4) and Zr(N2TBSNpy)(NMesN2NPh)] (5) by addition of phenyl azide, whereas the reaction of 2 or 3 with mesityl azide gave the alternative product 7, in which the azide is coupled with the CH activated ancillary tripod ligand. Reaction of 1 molar equiv of trimethylsilyl azide or 1-adamantyl azide with the previously reported hydrazinediido complex [Zr(N2TBSNpy)(═NNPh2)(py)] (9) at ambient temperature resulted in the formation of the five-membered zirconaacacycles [Zr(N2TBSNpy)(NTMSN3NPh2)] (10) and [Zr(N2TBSNpy)(NAdN3NPh2)] (11). Complex 11 was thermally converted into the diazenido complex 12 via loss of 1 molar equiv of molecular N2. The direct formation of the analogous side-on-bonded diazenido analogue 13 was observed upon reaction of 9 with 1 equiv of mesityl azide at ambient temperature. On the basis of 15N labeling and DFT modeling (DFT(B3PW91/6-31 g(d))) a mechanism for the reaction pathway leading to 12 and 13 is proposed.
Item Description:Gesehen am 26.04.2018
Physical Description:Online Resource
ISSN:1520-6041
DOI:10.1021/om300291b

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