Novel ansa-Metallocenes with a Single Boron Atom in the Bridge: Syntheses, Reactivities, and X-ray Structures of {Ph(L)B(η5-C5H4)2}ZrCl2 (L = SMe2, PMe3)
| Autor: | Arnold L. Rheingold, Daniel S. Stelck, and Pamela J. Shapiro, Naomi Basickes |
|---|---|
| Rok vydání: | 1997 |
| Předmět: |
chemistry.chemical_classification
Chemistry Stereochemistry Organic Chemistry Trimethylphosphine chemistry.chemical_element Crystal structure Alkylation Medicinal chemistry Adduct Inorganic Chemistry chemistry.chemical_compound Polymerization Nucleophile Physical and Theoretical Chemistry Boron Alkyl |
| Zdroj: | Organometallics. 16:4546-4550 |
| ISSN: | 1520-6041 0276-7333 |
| DOI: | 10.1021/om970253+ |
| Popis: | The syntheses and X-ray crystal structures of the boron-bridged ansa-metallocene complexes [{Ph(Me2S)B(η5-C5H4)2}ZrCl2]·C6D6 (2) and [{Ph(Me3P)B(η5-C5H4)2}ZrCl2] (3) are reported. Complex 2 is obtained as the product of a double dehalodesilylation reaction between PhB(C5H4SiMe3)2 and ZrCl4(SMe2)2. The dimethyl sulfide adduct of 2 is readily replaced with trimethylphosphine to afford 3. Efforts to alkylate 2 were unsuccessful, presumably due to the lability of the dimethyl sulfide and, hence, its inability to protect the boron bridge from nucleophilic attack by alkyl anions. In contrast, the trimethylphosphine adduct in 3 binds tightly enough to the boron bridge to protect it from nucleophilic attack. Also, unlike 2, complex 3 is activated by methylalumoxane toward the polymerization of ethylene. |
| Databáze: | OpenAIRE |
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