Fulvene to cyclopentadienyl conversion with homoleptic complexes of zirconium and hafnium
The reaction of 6,6-dimethylfulvene with M(CH{sub 2}Ph){sub 4} (M = Zr, Hf) in benzene gives [{eta}{sup 5}-C{sub 5}H{sub 4}(CMe{sub 2}CH{sub 2}Ph)]M(CH{sub 2}Ph){sub 3} (1, M = Zr; 2, M = Hf) without any observable byproducts. A similar reaction for M = Ti is not observed. The single-crystal X-ray study of 1 shows a three-legged piano-stool geometry with an {eta}{sup 2}-bound benzyl ligand. A second equivalent of 6,6-dimethylfulvene does not react with either 1 or 2. The bulkier 6,6-diphenyfulvene only reacts cleanly with the more Lewis acidic Hf(CH{sub 2}Ph){sub 4} to give [{eta}{sup 5}-C{sub 5}H{sub 4}(CPh{sub 2}CH{sub 2}Ph)]Hf(CH{sub 2}Ph){sub 3} (3). Using the tetraamido complexes M(NMe{sub 2}Ph){sub 4} and 6,6-dimethylfulvene, one obtains dimethylamine and [{eta}{sup 5}-C{sub 5}H{sub 4}(CMeCH{sub 2})]M(NMe{sub 2}){sub 3} (4 for M = Zr) in good yield. These products are formally derived from the deprotonation of a fulvene methyl group and subsequent coordination of the resulting 2-propenylcyclopentadienyl fragment. Reaction of 4 and 6,6-dimethylfulvene affords the bent metallocene [{eta}{sup 5}-C{sub 5}H{sub 4}(CMeCH{sub 2})]{sub 2}Zr(NMe{sub 2}){sub 2} (5). Excess 8,8-dimethylbenzofulvene and M(NMe{sub 2}){sub 4} provides exclusively the product with only one coordinated indene.
- Research Organization:
- Univ. of California, Santa Barbara, CA (US)
- Sponsoring Organization:
- American Chemical Society; US Department of Energy
- DOE Contract Number:
- FG03-98ER14910
- OSTI ID:
- 20013593
- Journal Information:
- Organometallics, Journal Name: Organometallics Journal Issue: 20 Vol. 18; ISSN ORGND7; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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