Dichlorobis(η
 5
 ‐Chlorocyclopentadienyl)‐Titanium, (ClC
 5
 H
 4
 )
 2
 TiCl
 2

Anslyn, Eric A.; Grubbs, Robert H.; Felten, Christian; Rehder, Dieter

doi:10.1002/9780470132609.ch48

“…Treatment of the known titanocene dichlorides (C 5 H 4 X)(C 5 H 4 Y)TiCl 2 (X = Y = H, 1a; X = H, Y = Cl, 1b; X = Y = Cl, 1c) [33,34] with HS-C 6 H 4 R (R = H, p-Me) in the presence of DABCO (1,4- alkyl lithiums to thermally unstable titanocene alkyls Cp2TiR2, which easily decompose to titanium(III) products [22,23] and with lithium amides to mono-cyclopentadienyl titanium tris-amides CpTi(NR2)3 [24]. In addition, with the often-used base KO t Bu, a mixture of products including those of splitting off the cyclopentadienyl ligands was observed [25].…”

Section: Synthesis Of Starting Materialsmentioning

confidence: 99%

“…Treatment of the known titanocene dichlorides (C5H4X)(C5H4Y)TiCl2 (X = Y = H, 1a; X = H, Y = Cl, 1b; X = Y = Cl, 1c) [33,34] with HS-C6H4R (R = H, p-Me) in the presence of DABCO…”

Section: Synthesis Of Starting Materialsmentioning

confidence: 99%

“…All reagents (n-BuLi: 1.6M in Hexane, thiophenol, thiocresol, Di-isopropylamine, hexachloroethane, dimethyldisulfide, and DABCO) and Cp 2 TiCl 2 were obtained from commercial suppliers and were used as such. (C 5 H 4 Cl)(C 5 H 4 X)TiCl 2 (X = H, Cl) were prepared according to literature procedures [33,34]. Fresh solutions of LDA were prepared from Di-isopropylamine and n-BuLi in THF.…”

Section: Experimental Partmentioning

confidence: 99%

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Metalation Studies on Titanocene Dithiolates

Kießling

¹

,

Sünkel

²

2018

Inorganics

1

0

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Titanocene bis-arylthiolates [(C5H4X)(C5H4Y)Ti(SC6H4R)2] (X,Y = H, Cl; R = H, Me) can be prepared from the corresponding titanocene dichlorides by reacting with the thiols in the presence of DABCO as a base. They react with n-butyl lithium to give unstable Ti(III) radical anions. While the unsubstituted thiolates (X = Y = R = H) react with lithium Di-isopropylamide by decomposing to dimeric fulvalene-bridged and thiolate-bridged Ti(III) compounds, the ring-chlorinated compounds can be deprotonated with LDA and give appropriate electrophiles di-substituted and tri-substituted titanocene dithiolates.

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Titanium: Organometallic Chemistry

Mintz

¹

2005

Encyclopedia of Inorganic Chemistry

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The majority of titanium organometallic chemistry involves complexes in which the titanium is in its highest oxidation state (+4) with cyclopentadienyl derivatives as ancillary ligands. However, considerable chemistry has also been developed for complexes with titanium in the +3 and +2 oxidation state, with lesser amounts of chemistry developed for titanium in lower oxidation states (+1, 0). Since the early 1980s, chemists have placed considerable emphasis on the fine‐tuning of the structure and reactivity of titanium organometallic complexes. Particular emphasis has been devoted to tailoring the structure and reactivity of bis(cyclopentadienyl)titanium derivatives by incorporating electron‐donating, electron‐withdrawing, sterically demanding, or chiral substituents on the cyclopentadienyl ring. Considerable effort has gone into preparing ansa‐metallocenes with a wide variety of bridging groups and substituents to fine‐tune the reactivity catalysts prepared from them. In a similar manner, considerable effort has gone into the development of constrained geometry complexes. Several types of chiral substituted cyclopentadienyl, annulated cyclopentadienyl, ansa ‐metallocenes, and constrained geometry complexes have been prepared and applied to olefin polymerization and organic synthesis. Additional efforts at modifying the structure and reactivity by focusing on varying the oxidation state or coordination geometry at the titanium center have expanded over the past decade.

show abstract

Titanium: Organometallic Chemistry

Mintz

¹

2005

Encyclopedia of Inorganic and Bioinorganic Chemistry

0

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The majority of titanium organometallic chemistry involves complexes in which the titanium is in its highest oxidation state (+4) with cyclopentadienyl derivatives as ancillary ligands. However, considerable chemistry has also been developed for complexes with titanium in the +3 and +2 oxidation state, with lesser amounts of chemistry developed for titanium in lower oxidation states (+1, 0). Since the early 1980s, chemists have placed considerable emphasis on the fine‐tuning of the structure and reactivity of titanium organometallic complexes. Particular emphasis has been devoted to tailoring the structure and reactivity of bis(cyclopentadienyl)titanium derivatives by incorporating electron‐donating, electron‐withdrawing, sterically demanding, or chiral substituents on the cyclopentadienyl ring. Considerable effort has gone into preparing ansa‐metallocenes with a wide variety of bridging groups and substituents to fine‐tune the reactivity catalysts prepared from them. In a similar manner, considerable effort has gone into the development of constrained geometry complexes. Several types of chiral substituted cyclopentadienyl, annulated cyclopentadienyl, ansa ‐metallocenes, and constrained geometry complexes have been prepared and applied to olefin polymerization and organic synthesis. Additional efforts at modifying the structure and reactivity by focusing on varying the oxidation state or coordination geometry at the titanium center have expanded over the past decade.

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Dichlorobis(η ⁵ ‐Chlorocyclopentadienyl)‐Titanium, (ClC ₅ H ₄ ) ₂ TiCl ₂

Cited by 6 publications

References 6 publications

Metalation Studies on Titanocene Dithiolates

Metalation Studies on Titanocene Dithiolates

Titanium: Organometallic Chemistry

Titanium: Organometallic Chemistry

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Dichlorobis(η 5 ‐Chlorocyclopentadienyl)‐Titanium, (ClC 5 H 4 ) 2 TiCl 2

Cited by 6 publications

References 6 publications

Metalation Studies on Titanocene Dithiolates

Metalation Studies on Titanocene Dithiolates

Titanium: Organometallic Chemistry

Titanium: Organometallic Chemistry

Contact Info

Product

Resources

About

Dichlorobis(η ⁵ ‐Chlorocyclopentadienyl)‐Titanium, (ClC ₅ H ₄ ) ₂ TiCl ₂