Synthesis and Structural Characterization of Azatitanacyclobutane Derivatives

Beckhaus, Rüdiger; Wagner, Martin F.‐X.; Wang, Ruimin

doi:10.1002/(sici)1099-0682(199802)1998:2<253::aid-ejic253>3.0.co;2-x

Cited by 17 publications

(5 citation statements)

References 25 publications

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“…Similarly, formal [2+2] cycloadditons of iron-, rhenium-, and manganese-vinylidene complexes with imines yield azetidinylidene derivatives. Azatitanacyclobutane complexes have been prepared by [2+2] cycloadditons of TiC and NC units …”

Section: Resultsmentioning

confidence: 99%

A Four-Electron π-Alkyne Complex as Precursor for Allenylidene Derivatives: Preparation, Structure, and Reactivity of [Os(η⁵-C₅H₅)(CCCPh₂)L(PⁱPr₃)]PF₆ (L = CO, PHPh₂)

et al. 2004

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2 (9). The allenylidene ligand of 4 undergoes the addition of carbodiimides to give iminiumazetidinylidenemethyl derivatives. The reaction with N,N′-dicyclohexylcarbodiimide affords [Os(η 5 -C 5 H 5 ){CHdCC(Ph) 2 N(Cy)+C+NdC(CH 2 ) 4 CH 2 }(CO)(P i Pr 3 )]PF 6 (10), whereas the reaction with N,N′-diisopropylcarbodiimide leads to [Os(η 5 -C 5 H 5 ){CHdCC(Ph) 2 N-( i Pr)+C+NdC(CH 3 ) 2 }(CO)(P i Pr 3 )]PF 6 (11). Complex 4 also reacts with methanol and aniline. The addition of methanol to the allenylidene 4 gives [Os(η 5 -C 5 H 5 ){C(OCH 3 )CHdCPh 2 }(CO)-(P i Pr 3 )]PF 6 (12), which undergoes deprotonation at the CHdCPh 2 group to afford Os(η 5 -C 5 H 5 ){C(OCH 3 )dCdCPh 2 }(CO)(P i Pr 3 ) (13). The addition of aniline leads to [Os(η 5 -C 5 H 5 )-{C(CHdCPh 2 )dNHPh}(CO)(P i Pr 3 )]PF 6 (14). Treatment of 14 with NaOCH 3 gives Os(η 5 -C 5 H 5 ){C(CHdCPh 2 )dNPh}(CO)(P i Pr 3 ) (15). Complexes 4, 7, and 8 have been characterized by X-ray diffraction analysis.

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Section: Resultsmentioning

confidence: 99%

A Four-Electron π-Alkyne Complex as Precursor for Allenylidene Derivatives: Preparation, Structure, and Reactivity of [Os(η⁵-C₅H₅)(CCCPh₂)L(PⁱPr₃)]PF₆ (L = CO, PHPh₂)

et al. 2004

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“…The three‐membered azatitanacycles IIIa are defined as η 2 ‐imine complexes . The four‐membered rings exist as azatitanacyclobutanes IVa or ‐butenes IVb, which can be generated via [2+2] cycloaddition reactions of olefins or alkynes– and titanium imido species, or by employing titanium carbenes and carbodiimides . The family of the five‐membered rings is represented by insertion products of olefins and acetylenes into titanaaziridines, leading to azatitanacylopentanes Va and −3‐pentenes Vb ,.…”

Section: Introductionmentioning

confidence: 99%

From Five to Seven: Ring Expansion of Monoazadiene Titanium Complexes by Insertion of Aldehydes, Ketones and Nitriles

Manßen

Kahrs

Töben

et al. 2017

Chemistry A European J

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The ring enlargement reactions at ambient temperatures of non C-terminus substituted monoazabutadiene (η -RN=CHCH=CH ) titanium complexes 2 are investigated. The insertion of aldehydes/ketones (five examples) and nitriles (four examples) into the Ti-C bonds result in expansion of the five-membered rings to uncommon seven-membered titanacycles 3 and 4 in good yields. These new compounds are fully characterized by NMR spectroscopy and single-crystal X-ray diffraction. In subsequent reactions, the seven-membered ring systems are protolyzed and the released organic fragments are isolated. Whereas the aldehyde/ketone insertion products 3 form substituted δ-amino alcohols 5 after reduction with NaBH CN, the nitrile insertion products 4 form substituted pyrroles 6 via cyclization.

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“…The product obtained can be described as a tetrazadimetallabicycle . The titanaallene intermediate [Cp* 2 TiCCH 2 ] was reacted with carbodiimides RNCNR′ (R, R′ = p -Tol, Cy) to give products, which display a four membered azatitanacyclobutene moiety formed via a formal [2 + 2] cycloaddition reaction …”

Section: Introductionmentioning

confidence: 99%

Reactions of Titanocene Bis(trimethylsilyl)acetylene Complexes with Carbodiimides: An Experimental and Theoretical Study of Complexation versus C–N Bond Activation

et al. 2012

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The reaction of the low valent metallocene(II) sources Cp'(2)Ti(η(2)-Me(3)SiC(2)SiMe(3)) (Cp' = η(5)-cyclopentadienyl, 1a or η(5)-pentamethylcyclopentadienyl, 1b) with different carbodiimide substrates RN═C═NR' 2-R-R' (R = t-Bu; R' = Et; R = R' = i-Pr; t-Bu; SiMe(3); 2,4,6-Me-C(6)H(2) and 2,6-i-Pr-C(6)H(3)) was investigated to explore the frontiers of ring strained, unusual four-membered heterometallacycles 5-R. The product complexes show dismantlement, isomerization, or C-C coupling of the applied carbodiimide substrates, respectively, to form unusual mono-, di-, and tetranuclear titanium(III) complexes. A detailed theoretical study revealed that the formation of the unusual complexes can be attributed to the biradicaloid nature of the unusual four-membered heterometallacycles 5-R, which presents an intriguing situation of M-C bonding. The combined experimental and theoretical study highlights the delicate interplay of electronic and steric effects in the stabilization of strained four-membered heterometallacycles, accounting for the isolation of the obtained complexes.

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Synthesis and Structural Characterization of Azatitanacyclobutane Derivatives

Cited by 17 publications

References 25 publications

A Four-Electron π-Alkyne Complex as Precursor for Allenylidene Derivatives: Preparation, Structure, and Reactivity of [Os(η⁵-C₅H₅)(CCCPh₂)L(PⁱPr₃)]PF₆ (L = CO, PHPh₂)

A Four-Electron π-Alkyne Complex as Precursor for Allenylidene Derivatives: Preparation, Structure, and Reactivity of [Os(η⁵-C₅H₅)(CCCPh₂)L(PⁱPr₃)]PF₆ (L = CO, PHPh₂)

From Five to Seven: Ring Expansion of Monoazadiene Titanium Complexes by Insertion of Aldehydes, Ketones and Nitriles

Reactions of Titanocene Bis(trimethylsilyl)acetylene Complexes with Carbodiimides: An Experimental and Theoretical Study of Complexation versus C–N Bond Activation

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Synthesis and Structural Characterization of Azatitanacyclobutane Derivatives

Cited by 17 publications

References 25 publications

A Four-Electron π-Alkyne Complex as Precursor for Allenylidene Derivatives: Preparation, Structure, and Reactivity of [Os(η5-C5H5)(CCCPh2)L(PiPr3)]PF6 (L = CO, PHPh2)

A Four-Electron π-Alkyne Complex as Precursor for Allenylidene Derivatives: Preparation, Structure, and Reactivity of [Os(η5-C5H5)(CCCPh2)L(PiPr3)]PF6 (L = CO, PHPh2)

From Five to Seven: Ring Expansion of Monoazadiene Titanium Complexes by Insertion of Aldehydes, Ketones and Nitriles

Reactions of Titanocene Bis(trimethylsilyl)acetylene Complexes with Carbodiimides: An Experimental and Theoretical Study of Complexation versus C–N Bond Activation

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A Four-Electron π-Alkyne Complex as Precursor for Allenylidene Derivatives: Preparation, Structure, and Reactivity of [Os(η⁵-C₅H₅)(CCCPh₂)L(PⁱPr₃)]PF₆ (L = CO, PHPh₂)

A Four-Electron π-Alkyne Complex as Precursor for Allenylidene Derivatives: Preparation, Structure, and Reactivity of [Os(η⁵-C₅H₅)(CCCPh₂)L(PⁱPr₃)]PF₆ (L = CO, PHPh₂)