FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2022657029> ?p ?o ?g. }

• W2022657029 endingPage "3334" @default.
• W2022657029 startingPage "3321" @default.
• W2022657029 abstract "Alkylation of the terminal neopentylidene titanium(IV) complex (L1)TiCHtBu(OTf) (L1- = [Ar]NC(Me)CHC(Me)N[Ar], Ar = 2,6-(CHMe2)2C6H3) with LiCH2SiMe3 resulted in formation of the alkylidene−alkyl species (L1)TiCHtBu(CH2SiMe3) (1) in 82% yield. Compound 1 was fully characterized, and the molecular structure disclosed a four-coordinate titanium complex having significant α-hydrogen agostic interaction and possessing terminal alkylidene and alkyl functionalities. Attempts to alkylate (L1)TiCHtBu(OTf) with KCH2Ph in THF resulted in clean deprotonation of the methyl group attached to the β-carbon of the diketiminate ligand to form the four-coordinate titanium(IV) neopentylidene−tetrahydrofuran complex (L2)TiCHtBu(THF) (2; L22- = [Ar]NC(Me)CH(CH2)N[Ar], 64% isolated yield). Complex 2 was fully characterized and revealed a low-coordinate titanium(IV) in a C1 environment, which is supported by a chelating bis-anilide ligand. Alkylation of the alkylidene derivative (L3)TiCHtBu(OTf) (L3- = [Ar]NC(tBu)CHC(tBu)N[Ar], Ar = 2,6-(CHMe2)2C6H3) with LiCH2SiMe3 or KCH2Ph resulted in clean formation of (L3)TiCHtBu(R) (R = CH2SiMe3 (3), CH2Ph (4)). Complexes 3 and 4 were fully characterized, and the structure of 4 was determined by single-crystal X-ray diffraction studies. Complex 1 was found to decompose rapidly to several products, of which the titanacycle Ti[2,6-(CMe2)(CHMe2)C6H3]NC(Me)CHC(Me)N[2,6-(CMe2)(CHMe2)C6H3](CH2Si(Me)3) (5) and dimer [TiNAr([Ar]NC(Me)CHC(μ-CH2)CHtBu)]2 (6) were formed. Complex 5 was prepared in better yield through an independent synthesis involving Ti[2,6-(CMe2)(CHMe2)C6H3]NC(Me)CHC(Me)N[2,6-(CMe2)(CHMe2)C6H3](OTf) and LiCH2SiMe3. In THF complex 6 dissociated into the corresponding monomer (tBuHCC(CH2)CHC(CH3)N[Ar])TiNAr(THF) (8), quantitatively. Unlike complex 1, complexes 3 and 4 are kinetically more stable to intramolecular Wittig-like and C−H abstraction reactions. It was also found that one-electron reduction of the four-coordinate titanium alkylidene complexes (L1)TiCHtBu(OTf) and (L3)TiCHtBu(OTf) afforded the Ti(III) metallacycles ([Ar]NC(R)CHC(R)N[2,6-(CHMe2)(CH(CH2)(Me))C6H3])TiCH2tBu (L42-, R = Me (9); L52-, R = tBu (10)), both resulting from 1,2-addition of the proximal isopropyl CH3 group across the TiCHtBu bond. One-electron oxidation of 10 with AgOTf promotes α-abstraction to generate back the alkylidene precursor (L3)TiCHtBu(OTf). The redox-controlled 1,2-addition and α-abstraction reactions are specific only to the isopropyl methyl attached to the aryl group of the β-diketiminate ligand." @default.
• W2022657029 created "2016-06-24" @default.
• W2022657029 creator A5051328139 @default.
• W2022657029 creator A5064960434 @default.
• W2022657029 creator A5073811804 @default.
• W2022657029 creator A5080206718 @default.
• W2022657029 date "2005-05-26" @default.
• W2022657029 modified "2023-10-09" @default.
• W2022657029 title "Intramolecular C−H Activation Reactions Derived from a Terminal Titanium Neopentylidene Functionality. Redox-Controlled 1,2-Addition and α-Hydrogen Abstraction Reactions" @default.
• W2022657029 cites W1969958859 @default.
• W2022657029 cites W1970659055 @default.
• W2022657029 cites W1979303449 @default.
• W2022657029 cites W1980290845 @default.
• W2022657029 cites W1981730841 @default.
• W2022657029 cites W1982618234 @default.
• W2022657029 cites W1982791686 @default.
• W2022657029 cites W1983512172 @default.
• W2022657029 cites W1984208588 @default.
• W2022657029 cites W1985565100 @default.
• W2022657029 cites W1988594523 @default.
• W2022657029 cites W1995623672 @default.
• W2022657029 cites W1996138125 @default.
• W2022657029 cites W1996151069 @default.
• W2022657029 cites W1996387511 @default.
• W2022657029 cites W2000466466 @default.
• W2022657029 cites W2001011492 @default.
• W2022657029 cites W2005661768 @default.
• W2022657029 cites W2013825004 @default.
• W2022657029 cites W2016551454 @default.
• W2022657029 cites W2016673663 @default.
• W2022657029 cites W2019132898 @default.
• W2022657029 cites W2020824700 @default.
• W2022657029 cites W2030340979 @default.
• W2022657029 cites W2037739589 @default.
• W2022657029 cites W2039579891 @default.
• W2022657029 cites W2043510643 @default.
• W2022657029 cites W2054149576 @default.
• W2022657029 cites W2074127445 @default.
• W2022657029 cites W2081405235 @default.
• W2022657029 cites W2095989750 @default.
• W2022657029 cites W2153725588 @default.
• W2022657029 cites W286513275 @default.
• W2022657029 cites W4241539862 @default.
• W2022657029 doi "https://doi.org/10.1021/om049318g" @default.
• W2022657029 hasPublicationYear "2005" @default.
• W2022657029 type Work @default.
• W2022657029 sameAs 2022657029 @default.
• W2022657029 citedByCount "46" @default.
• W2022657029 countsByYear W20226570292012 @default.
• W2022657029 countsByYear W20226570292013 @default.
• W2022657029 countsByYear W20226570292014 @default.
• W2022657029 countsByYear W20226570292015 @default.
• W2022657029 countsByYear W20226570292016 @default.
• W2022657029 countsByYear W20226570292017 @default.
• W2022657029 countsByYear W20226570292018 @default.
• W2022657029 countsByYear W20226570292019 @default.
• W2022657029 countsByYear W20226570292020 @default.
• W2022657029 countsByYear W20226570292021 @default.
• W2022657029 countsByYear W20226570292022 @default.
• W2022657029 countsByYear W20226570292023 @default.
• W2022657029 crossrefType "journal-article" @default.
• W2022657029 hasAuthorship W2022657029A5051328139 @default.
• W2022657029 hasAuthorship W2022657029A5064960434 @default.
• W2022657029 hasAuthorship W2022657029A5073811804 @default.
• W2022657029 hasAuthorship W2022657029A5080206718 @default.
• W2022657029 hasConcept C116569031 @default.
• W2022657029 hasConcept C118629725 @default.
• W2022657029 hasConcept C145148216 @default.
• W2022657029 hasConcept C155647269 @default.
• W2022657029 hasConcept C161790260 @default.
• W2022657029 hasConcept C164361826 @default.
• W2022657029 hasConcept C170493617 @default.
• W2022657029 hasConcept C178790620 @default.
• W2022657029 hasConcept C185592680 @default.
• W2022657029 hasConcept C188328357 @default.
• W2022657029 hasConcept C2776568683 @default.
• W2022657029 hasConcept C2776701986 @default.
• W2022657029 hasConcept C2779546866 @default.
• W2022657029 hasConcept C2780263894 @default.
• W2022657029 hasConcept C2780471494 @default.
• W2022657029 hasConcept C544153396 @default.
• W2022657029 hasConcept C55493867 @default.
• W2022657029 hasConcept C71240020 @default.
• W2022657029 hasConcept C75079739 @default.
• W2022657029 hasConcept C8010536 @default.
• W2022657029 hasConceptScore W2022657029C116569031 @default.
• W2022657029 hasConceptScore W2022657029C118629725 @default.
• W2022657029 hasConceptScore W2022657029C145148216 @default.
• W2022657029 hasConceptScore W2022657029C155647269 @default.
• W2022657029 hasConceptScore W2022657029C161790260 @default.
• W2022657029 hasConceptScore W2022657029C164361826 @default.
• W2022657029 hasConceptScore W2022657029C170493617 @default.
• W2022657029 hasConceptScore W2022657029C178790620 @default.
• W2022657029 hasConceptScore W2022657029C185592680 @default.
• W2022657029 hasConceptScore W2022657029C188328357 @default.
• W2022657029 hasConceptScore W2022657029C2776568683 @default.
• W2022657029 hasConceptScore W2022657029C2776701986 @default.
• W2022657029 hasConceptScore W2022657029C2779546866 @default.

• next