Monoazadien-Komplexe elektronenarmer Übergangsmetalle, I. Zirconocen(1-aza-1,3-dien)1-Komplexe: Synthese, Struktur und Reaktionen

✍ Scribed by Scholz, Joachim ;Nolte, Matthias ;Krüger, Carl

• Publisher: Wiley (John Wiley & Sons)
• Year: 1993
• Tongue: English
• Weight: 797 KB
• Volume: 126
• Category: Article
• ISSN: 0009-2940
• DOI: 10.1002/cber.19931260335

✦ Synopsis

Homoenolate equivalent

Monoazadiene

Complexes of Electron-Deficient Transition Metals, I. -Zirconocene(1-aza-1.3-diene) Complexes: Synthesis, Structure and Reactions['1

The reduction of CpzZrClz in THF by Mg in the presence of l-aza-1,3-dienes 2ad generates the orange air-sensitive zirconocene(s-cis-l-aza-1,3-diene) complexes 3ad. 'H-and I3C-NMR spectral data of 3ad indicate that the bonding of the heterodiene ligand has 02,x-metallacyclopentene rather than q4-l-aza-1,3-diene character. No evidence for s-trans-heterodiene coordination was found in any of the new zirconocene complexes. The molecular structure of 3d has been deter-mined by single-crystal X-ray diffraction, confirming the envelope-shaped 02,x-type structure also in the solid state. 3b slowly reacts with one molar equivalent of acetophenone to give a seven-membered oxaazametallacycle Cp,Zr(NRCH = CHCHPhC(Me)PhO) (4) which has a cis-C = C bond in the ring. The structure of 4 has been determined by NMR and X-ray diffraction.