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

• Verfasst von: Gehrmann, Thorsten [VerfasserIn]
• Verfasst von: Lloret Fillol, Julio [VerfasserIn]
• Verfasst von: Wadepohl, Hubert [VerfasserIn]
• Verfasst von: Gade, Lutz H. [VerfasserIn]
• Titel: Synthesis, characterization, and thermal rearrangement of zirconium tetraazadienyl and pentaazadienyl complexes
• Verf.angabe: Thorsten Gehrmann, Julio Lloret Fillol, Hubert Wadepohl, and Lutz H. Gade
• E-Jahr: 2012
• Jahr: June 4, 2012
• Umfang: 12 S.
• Fussnoten: Gesehen am 26.04.2018
• Titel Quelle: Enthalten in: Organometallics
• Ort Quelle: Washington, DC : ACS Publ., 1982
• Jahr Quelle: 2012
• Band/Heft Quelle: 31(2012), 12, Seite 4504-4515
• ISSN Quelle: 1520-6041
• DOI: doi:10.1021/om300291b
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1572389974

Abstract

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.