The synthesis of group IV metallocene dichlorides with variable sterics, conformational mobility and geometric shapes.
| dc.contributor.author | Combs, David. | en_US |
| dc.date.accessioned | 2013-08-16T12:29:56Z | |
| dc.date.available | 2013-08-16T12:29:56Z | |
| dc.date.issued | 1997 | en_US |
| dc.description.abstract | New chiral doubly bridged bis(tetrahydroindenyl)zirconium dichloride 285 has been synthesized from chiral doubly bridged 284 in excellent yield. These complexes give access to rigid ansa-bis(indenyl)- and ansa-bis(tetrahydroindenyl)zirconium dichlorides. The structures of 284 and 285 were determined by X-ray diffraction and have confirmed the closed shape of these metallocene dichlorides. | en_US |
| dc.description.abstract | We have prepared several novel metallocene dichlorides bridged at the $7,7\sp\prime$ position of the indenyl moiety. The new metal complexes include the methylene bridged dl-bis(4,6-dimethylinden-7-yl) methylidenetitanium dichloride 349, and dl-bis(4,6-dimethylinden-7-yl)$\rbrack$methylidenezirconium dichloride 348 which were prepared from m-xylene. In addition, dl-1,2-bis(4-methylinden-7-yl)$\rbrack$ethylidene, dl-1,2-bis(4-isopropylinden-7-yl)$\rbrack$ethylidenezirconium dichlorides (dl-339) and (dl-340) and dl-1,2-bis(4-isopropylinden-7, yl)$\rbrack$ethylidenetitanium dichloride (dl-341) were synthesized from p-cymene and p-xylene, respectively. The structure of metallocene dichlorides dl-339, dl-340, and dl-341 were determined by X-ray crystallography and found to have $\rm C\sb1$-symmetry in the solid state, but in solution exhibit $\rm C\sb2$-symmetry as seen in their $\rm\sp1 H$ NMR spectra at room temperature. The synthesis of these new titanocene and zirconocene dichlorides will be discussed. | en_US |
| dc.description.abstract | $2,2\sp\prime$-$\rm Bis\lbrack 1$-(4,7-dimethyl-indenylmethyl)) -$1,1\sp\prime$-binaphthyltitanium and -zirconium dichlorides have been synthesized from $2,2\sp\prime$-bis(bromomethyl)-$1,1\sp\prime$-binaphthalene 221. $2,2\sp\prime$-Bis(bromomethyl)-$1,1\sp\prime$-binaphthalene 221 was alkylated with 4,7-dimethylindene 229 to yield $2,2\sp\prime$-$\rm bis\lbrack 1$-(4,7-dimethyl-indenylmethyl)$\rbrack$-$1,1\sp\prime$-binaphth alene (S)-(${\bf -}$)-212. The dilithio salts were formed and metallated with titanium trichloride and zirconium tetrachloride to give ansa-$\rm bis\lbrack 1$-(4,7-dimethyl-indenylmethyl)$\rbrack$-$1,1\sp\prime$-binaphth yltitanium dichloride (S)-(+)-232 and -zirconium dichloride 233. | en_US |
| dc.format.extent | xvi, 151 leaves : | en_US |
| dc.identifier.uri | http://hdl.handle.net/11244/5579 | |
| dc.note | Source: Dissertation Abstracts International, Volume: 58-12, Section: B, page: 6580. | en_US |
| dc.subject | Chemistry, Organic. | en_US |
| dc.subject | Catalysis. | en_US |
| dc.subject | Chirality. | en_US |
| dc.subject | Metallocenes Synthesis. | en_US |
| dc.thesis.degree | Ph.D. | en_US |
| dc.thesis.degreeDiscipline | Department of Chemistry and Biochemistry | en_US |
| dc.title | The synthesis of group IV metallocene dichlorides with variable sterics, conformational mobility and geometric shapes. | en_US |
| dc.type | Thesis | en_US |
| ou.group | College of Arts and Sciences::Department of Chemistry and Biochemistry | |
| ou.identifier | (UMI)AAI9817711 | en_US |
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