Metallocenes 1998
DOI: 10.1002/9783527619542.ch4
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Titanocenes

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Cited by 20 publications
(9 citation statements)
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“…Recently, we have become interested in the chemistry of the tris(trimethylsilyl)hydrazinodichlorophosphine, (Me 3 Si) 2 NN(SiMe 3 )PCl 2 ( 1 ), especially in its kinetic stability due to the presence of the bulky (Me 3 Si) 2 NN(SiMe 3 ) substituent on the phosphorus atom and in the elimination of Me 3 SiCl triggered by the action of Lewis acids such as GaCl 3 . It was of interest to study the reaction of 1 with low-coordinate, highly reactive transition metal complexes such as titanocene “Cp 2 Ti”, a species that, however, cannot be isolated. A useful approach to generate “Cp 2 Ti” utilizes the weak alkyne complex Cp 2 Ti(btmsa) [btmsa = bis(trimethylsilyl)acetylene (Me 3 Si)CC(SiMe 3 )] from which this unstable species can be generated under mild conditions by quantitative removal of the weakly bound alkyne ligand. A wide range of applications of Cp 2 Ti(btmsa) as stoichiometric reagent or catalyst has been developed …”
Section: Introductionmentioning
confidence: 99%
“…Recently, we have become interested in the chemistry of the tris(trimethylsilyl)hydrazinodichlorophosphine, (Me 3 Si) 2 NN(SiMe 3 )PCl 2 ( 1 ), especially in its kinetic stability due to the presence of the bulky (Me 3 Si) 2 NN(SiMe 3 ) substituent on the phosphorus atom and in the elimination of Me 3 SiCl triggered by the action of Lewis acids such as GaCl 3 . It was of interest to study the reaction of 1 with low-coordinate, highly reactive transition metal complexes such as titanocene “Cp 2 Ti”, a species that, however, cannot be isolated. A useful approach to generate “Cp 2 Ti” utilizes the weak alkyne complex Cp 2 Ti(btmsa) [btmsa = bis(trimethylsilyl)acetylene (Me 3 Si)CC(SiMe 3 )] from which this unstable species can be generated under mild conditions by quantitative removal of the weakly bound alkyne ligand. A wide range of applications of Cp 2 Ti(btmsa) as stoichiometric reagent or catalyst has been developed …”
Section: Introductionmentioning
confidence: 99%
“…Low-valent group 4 metallocene species such as “Cp 2 Zr” and “Cp 2 Ti” have played an important role in a variety of stoichiometric and catalytic reactions. A large number of examples dealing with coupling and cyclization of alkynes by zirconocene “Cp 2 Zr” and titanocene “Cp 2 Ti” have been well documented in the literature. Generally, the reaction pathway depends on the nature of the metallocene including the substitution pattern of the η 5 -cyclopentadienyl rings, the substituents of the alkynes, and the metal-to-alkyne ratio . The excellent work reported by Rosenthal and co-workers that described the reactivity of zirconocene “Cp 2 Zr” and titanocene “Cp 2 Ti” toward different diynes, especially 1,3-butadiynes, demonstrates how the combination of the metal, the substituent of the diynes, and the metal-to-diyne ratio could lead to fascinating compounds. , Si-tethered diynes, as reported by Takahashi, Mach, Rosenthal, et al, could also react with zirconocene “Cp 2 Zr” and titanocene “Cp 2 Ti” to afford unusual structures depending on the metal, the Cp ring, the substituents of the diynes, and the metal-to-diyne ratio …”
Section: Introductionmentioning
confidence: 99%
“…Despite the seemingly strong analogy between the Cp and the Cp* moieties, these ligands have a large effect on the reactivity of the (permethyl-)metallocene complexes. The replacement of hydrogen atoms by methyl substituents changes the steric and electronic influence of the ligand . As a result of increased steric bulk, higher solubility and the electron donor characteristics, different reactivities and spectral properties were found in the Cp* complexes compared to their Cp counterparts.…”
Section: Introductionmentioning
confidence: 99%