Regioselective reactions of isothiocyanates with the titanocene vinylidene fragment [Ti(CCH2)(η-C5Me 5)2]. Crystal and molecular structure of [Ti{SC(NC6H11)C CH2}(η-C5Me5 )2]

Beckhaus, Rüdiger; Sang, Javier; Wagner, Trixie; Böhme, Uwe

doi:10.1039/a701499f

“…101 Constrained geometry complexes with other π ligands have also been prepared. Treatment of (4-Dimethylsilyl-tertbutylamido)-N ,N -diisopropyl-1-aminoboratabenzene with two equivalents of t-BuLi followed by treatment with TiCl 4 gives (4-Dimethylsilyl-tert-butylamido)-N ,N -diisopropyl-1-aminoboratabenzene titanium dichloride complexes (46). 210 Treatment of TiCl 3 THF 3 with dianions (47) at low temperature followed by PbCl 2 gives the corresponding constrained geometry complexes (48) …”

Section: Ti CLmentioning

confidence: 99%

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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“…18 The Ti−S bond lengths as well as the S−C bond lengths lie in the range of single bonds. 19 The N2−C31 bond length (1.296 Å) is typical of N−C sp 2 double bonds, whereas the N1−N2 bond length between both nitrogen atoms at 1.4479 Å is in the range of nitrogen−nitrogen single bonds. 20 In the reaction of 2 with carbon monoxide (Scheme 6) in nhexane at ambient temperature the formation of the titanium monocyanate 6 is observed.…”

Section: ■ Introductionmentioning

confidence: 99%

Direct Access to Terminal Titanocene Hydrazides via Bis(η⁵:η¹-pentafulvene)titanium Complexes and 1,1-Diphenylhydrazine

Manßen

¹

,

Meyer

²

,

Schmidtmann

³

et al. 2018

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The formation of the titanocene hydrazido complex 2 via double N−H bond activations at ambient temperature of 1,1-diphenylhydrazine by the use of bis(η 5 :η 1adamantylidenepentafulvene)titanium complex 1 have been investigated. Starting from the titanium hydrazido complex 2, [2 + 2] cycloaddition and bond activation reactions are realized. In reaction with carbodiimides, the asymmetric N,N-bound ureato(2−) product 3 is observed. By use of nitriles, in addition to the [2 + 2] cycloaddition, the insertion of a second equivalent of the nitrile into the Ti−N bond is found (4). By reaction of 2 with carbon disulfide the symmetric S,S-bound thioureato(2−) complex 5 is isolated, whereas in reaction with carbon monoxide the cleavage of the N−N bond of the hydrazide unit is observed, resulting in the formation of the titanocene monocyanate 6. In contrast to the [2 + 2] cycloaddition reactions, for sterically demanding boranes such as 9-borabicyclo[3.3.1]nonane and catecholborane the hydroboration of the TiN double bond is observed, leading to the titanocene hydride complex 7 and the titanium(III) cation 8.

show abstract

Titanium: Organometallic Chemistry

Mintz

¹

2005

Encyclopedia of Inorganic Chemistry

View full text Add to dashboard Cite

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

Regioselective reactions of isothiocyanates with the titanocene vinylidene fragment [Ti(CCH2)(η-C5Me 5)2]. Crystal and molecular structure of [Ti{SC(NC6H11)C CH2}(η-C5Me5 )2]

Abstract: Complex a b c d e Ref.

Cited by 13 publications

References 47 publications

Titanium: Organometallic Chemistry

Titanium: Organometallic Chemistry

Direct Access to Terminal Titanocene Hydrazides via Bis(η⁵:η¹-pentafulvene)titanium Complexes and 1,1-Diphenylhydrazine

Titanium: Organometallic Chemistry

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Regioselective reactions of isothiocyanates with the titanocene vinylidene fragment [Ti(CCH2)(η-C5Me 5)2]. Crystal and molecular structure of [Ti{SC(NC6H11)C CH2}(η-C5Me5 )2]

Abstract: Complex a b c d e Ref.

Cited by 13 publications

References 47 publications

Titanium: Organometallic Chemistry

Titanium: Organometallic Chemistry

Direct Access to Terminal Titanocene Hydrazides via Bis(η5:η1-pentafulvene)titanium Complexes and 1,1-Diphenylhydrazine

Titanium: Organometallic Chemistry

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Direct Access to Terminal Titanocene Hydrazides via Bis(η⁵:η¹-pentafulvene)titanium Complexes and 1,1-Diphenylhydrazine