Crystal structure of an isomeric bis[(η
 5:η
 1-6,6-di-p-tolylpentafulvene)(η
 5-pentamethylcyclopentadienyl)titanium(III)]-μ
 2,η
 1:η
 1-dinitrogen complex, C60H66N2Ti2

Oswald, Tim; Frey, Annika; Schmidtmann, Marc; Beckhaus, Rüdiger

doi:10.1515/ncrs-2016-0074

Cited by 4 publications

(2 citation statements)

References 14 publications

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“…In aromatic solvents this rearrangement occurs at room temperature, whereas in aliphatic solvents higher temperatures are necessary (>80 °C). This type of 1,3-H shift has also been observed for other phenylfulvene titanium complexes …”

Section: Resultssupporting

confidence: 80%

“…This type of 1,3-H shift has also been observed for other phenylfulvene titanium complexes. 20 The monamides 2a−f have been fully characterized by NMR measurements (Table 1). Of high diagnostic value are the 1 H signals of the protonated exocyclic fulvene carbon atom in the range of 5 ppm ( 13 C, 52 ppm) and eight multiplets for the nonequivalent cyclopentadienyl and fulvene protons between 3.7 and 6.8 ppm.…”

Section: ■ Introductionmentioning

confidence: 99%

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Reactions of Secondary Amines with Bis(η⁵:η¹-pentafulvene)titanium Complexes: Formation of Titanium Amides and Titanaaziridines

et al. 2017

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The reactions of bis(η5:η1-pentafulvene)titanium complexes (1) with 19 different secondary amines (Aa–s) have been investigated. Depending on the substitution pattern of 1 and nature of the amine used, different reaction products are formed. With use of bis(η5:η1-di(p-tolyl)pentafulvene)titanium (1b) and N-methylanilines (Aa,b), N-methylbenzylamines (Ac,d), N-methylcyclohexylamine (Ae), and dibenzylamine (Af), titanium monoamides of the type (η5-C5H4CH(p-tolyl)2)(η5:η1-C5H4C(p-tolyl)2TiNR2 (2a–f) have been isolated in high yields and characterized, including by single-crystal X-ray diffraction. By the reactions of bis(η5:η1-adamantylidene)titanium (1a) and Af, diethylamine (Ag), and 2-methylpiperidine (Ah) similar monoamides 3f–h are formed. The formation of titanium bis-amides employing different types of secondary amines (Aa–s) is not observed. The formation of titanaaziridines is observed exclusively by using 1a and N-methylanilines (Aa,b), N-benzylphenylamine (Ai), and N-benzyltrimethylsilylamines (Aj,k). The titanaaziridine 4i undergoes a regioselective ring enlargement reaction with 1-hexyne. By the reaction of 4i and phenylacetylene a ring opening with formation of (CpAd)2Ti(NPh(CH2Ph)CCPh) (6) is observed. The acetylide 6 undergoes a thermal decomposition to give the zigzag butadiyne complex 7. In addition to the ring enlargement of 4j by ketones a ketone insertion in the titanium–Cp bond is found, as proved for 8 by single-crystal X-ray diffraction.

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Section: Resultssupporting

confidence: 80%

Section: ■ Introductionmentioning

confidence: 99%

Reactions of Secondary Amines with Bis(η⁵:η¹-pentafulvene)titanium Complexes: Formation of Titanium Amides and Titanaaziridines

et al. 2017

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Cyclopentadienyl and Phospholyl Complexes of the Group 4 Metals

Kilpatrick

Chadwick

2022

Comprehensive Organometallic Chemistry IV

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Pentafulvene complexes of group four metals: Versatile organometallic building blocks

Beckhaus

2018

Coordination Chemistry Reviews

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Crystal structure of an isomeric bis[(η ⁵:η ¹-6,6-di-p-tolylpentafulvene)(η ⁵-pentamethylcyclopentadienyl)titanium(III)]-μ ²,η ¹:η ¹-dinitrogen complex, C₆₀H₆₆N₂Ti₂

Abstract: CCDC no.: 1485820The title complex is shown in the gure. Tables 1 and 2 contain details of the measurement method and a list of the atoms including atomic coordinates and displacement parameters.

Cited by 4 publications

References 14 publications

Reactions of Secondary Amines with Bis(η⁵:η¹-pentafulvene)titanium Complexes: Formation of Titanium Amides and Titanaaziridines

Reactions of Secondary Amines with Bis(η⁵:η¹-pentafulvene)titanium Complexes: Formation of Titanium Amides and Titanaaziridines

Cyclopentadienyl and Phospholyl Complexes of the Group 4 Metals

Pentafulvene complexes of group four metals: Versatile organometallic building blocks

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Crystal structure of an isomeric bis[(η 5:η 1-6,6-di-p-tolylpentafulvene)(η 5-pentamethylcyclopentadienyl)titanium(III)]-μ 2,η 1:η 1-dinitrogen complex, C60H66N2Ti2

Abstract: CCDC no.: 1485820The title complex is shown in the gure. Tables 1 and 2 contain details of the measurement method and a list of the atoms including atomic coordinates and displacement parameters.

Cited by 4 publications

References 14 publications

Reactions of Secondary Amines with Bis(η5:η1-pentafulvene)titanium Complexes: Formation of Titanium Amides and Titanaaziridines

Reactions of Secondary Amines with Bis(η5:η1-pentafulvene)titanium Complexes: Formation of Titanium Amides and Titanaaziridines

Cyclopentadienyl and Phospholyl Complexes of the Group 4 Metals

Pentafulvene complexes of group four metals: Versatile organometallic building blocks

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Product

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Crystal structure of an isomeric bis[(η ⁵:η ¹-6,6-di-p-tolylpentafulvene)(η ⁵-pentamethylcyclopentadienyl)titanium(III)]-μ ²,η ¹:η ¹-dinitrogen complex, C₆₀H₆₆N₂Ti₂

Reactions of Secondary Amines with Bis(η⁵:η¹-pentafulvene)titanium Complexes: Formation of Titanium Amides and Titanaaziridines

Reactions of Secondary Amines with Bis(η⁵:η¹-pentafulvene)titanium Complexes: Formation of Titanium Amides and Titanaaziridines