Dimethyltitanocene

Payack, Joseph F.; Hughes, David L.; Cai, D.; Cottrell, Ian F.; Verhoeven, Thomas R.

doi:10.1002/0471264180.os079.03

Cited by 29 publications

(37 citation statements)

References 13 publications

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“…[25,26] The signals of the alkyne carbonsC 2a nd C3 (d C = 88.5 and 83.2 ppm, respectively), absent in the DEPT-135 NMR spectrum ( Figure 4b), fit againr easonablyw ell with other propargyl organometallics (Scheme 4).…”

Section: Propargyl Titanium Speciesmentioning

confidence: 71%

“…This feature indirectly supports the η 1 ‐coordination fashion of the propargyl moiety. Similar 13 C chemical shifts for alpha titanocenic carbons have been previously observed for [TiClCp 2 Me] and [TiCp 2 Me 2 ] with δ C =49.3 and 45.6 ppm, respectively . The signals of the alkyne carbons C2 and C3 ( δ C =88.5 and 83.2 ppm, respectively), absent in the DEPT‐135 NMR spectrum (Figure b), fit again reasonably well with other propargyl organometallics (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

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Unprecedented Spectroscopic and Computational Evidence for Allenyl and Propargyl Titanocene(IV) Complexes: Electrophilic Quenching of Their Metallotropic Equilibrium

Ruiz-Muelle

Oña‐Burgos

Ortuño

et al. 2016

Chemistry A European J

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The synthesis and structural characterization of allenyl titanocene(IV) [TiClCp2 (CH=C=CH2 )] 3 and propargyl titanocene(IV) [TiClCp2 (CH2 -C≡C-(CH2 )4 CH3 )] 9 have been described for the first time. Advanced NMR methods including diffusion NMR methods (diffusion pulsed field gradient stimulated spin echo (PFG-STE) and DOSY) have been applied and established that these organometallics are monomers in THF solution with hydrodynamic radii (from the Stokes-Einstein equation) of 3.5 and 4.1 Å for 3 and 9, respectively. Full (1) H, (13) C, Δ(1) H, and Δ(13) C NMR data are given, and through the analysis of the Ramsey equation, the first electronic insights into these derivatives are provided. In solution, they are involved in their respective metallotropic allenyl-propargyl equilibria that, after quenching experiments with aromatic and aliphatic aldehydes, ketones, and protonating agents, always give the propargyl products P (when carbonyls are employed), or allenyl products A (when a proton source is added) as the major isomers. In all the cases assayed, the ratio of products suggests that the metallotropic equilibrium should be faster than the reactions of 3 and 9 with electrophiles. Indeed, DFT calculations predict lower Gibbs energy barriers for the metallotropic equilibrium, thus confirming dynamic kinetic resolution.

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Section: Propargyl Titanium Speciesmentioning

confidence: 71%

Section: Resultsmentioning

confidence: 99%

Unprecedented Spectroscopic and Computational Evidence for Allenyl and Propargyl Titanocene(IV) Complexes: Electrophilic Quenching of Their Metallotropic Equilibrium

Ruiz-Muelle

Oña‐Burgos

Ortuño

et al. 2016

Chemistry A European J

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“…It is known that Cp protons in the titanocene(II) and zirconocene(II) complexes of a p-coordinated alkene or alkyne appear in the upper magnetic field compared to the dialkyltitanocenes(IV) and zirconocenes(IV) [32][33][34]. Carbons attached to Ti metals are commonly observed at lower field compared with the corresponding Zr and Hf compounds [35][36][37]. It may be noted that the coupling constants ( 1 J CH ) at C1 are larger in the Ti complexes than in the corresponding Zr and Hf complexes.…”

Section: Synthesis Of 1-hafnacyclopent-3-yne Complexesmentioning

confidence: 99%

Synthesis and structure of 1-metallacyclopent-3-yne complexes of group 4 metals

Suzuki

Watanabe

Yoshida

et al. 2006

Journal of Organometallic Chemistry

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“…The subsequent steps involve active TiC species. It may be noted that, TiC bond is stable in aqueous medium in many compounds like those in [Cp 2 TiMe 2 ] 42. In addition, since the polymerization takes place inside the micelles, the reaction environment is largely hydrophobic in nature.…”

Section: Resultsmentioning

confidence: 99%

Titanium(IV) nonmetallocene complex catalyzed aqueous homopolymerization and copolymerization of styrene and methyl methacrylate: An Environmentally friendly approach to ultrahigh molecular weight polymer nanoparticles

Bhattacharjee

2013

J. Polym. Sci. A Polym. Chem.

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A new titanium(IV) complex bearing [ONO] type ligand has been synthesized, characterized, and employed as catalyst in homopolymerization and copolymerization of styrene and methyl methacrylate. In the presence of sodium tetraphenyl borate and sodium n-dodecyl sulfate (SDS), it exhibits moderate to high activity and afford ultrahigh molecular weight polymers. V C 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 1540-1549

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Dimethyltitanocene

Abstract: Dimethyltitanocene R Titanocene dichloride P Dimethyltitanocene

Cited by 29 publications

References 13 publications

Unprecedented Spectroscopic and Computational Evidence for Allenyl and Propargyl Titanocene(IV) Complexes: Electrophilic Quenching of Their Metallotropic Equilibrium

Unprecedented Spectroscopic and Computational Evidence for Allenyl and Propargyl Titanocene(IV) Complexes: Electrophilic Quenching of Their Metallotropic Equilibrium

Synthesis and structure of 1-metallacyclopent-3-yne complexes of group 4 metals

Titanium(IV) nonmetallocene complex catalyzed aqueous homopolymerization and copolymerization of styrene and methyl methacrylate: An Environmentally friendly approach to ultrahigh molecular weight polymer nanoparticles

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