Synthesis and reactions of new 1,2- and 1,3-cyclopentadienyl disubstituted cobalt sandwich compounds (η5-C5H3R2)Co(η4-C4Ph4) (R CH2OH, CHO, C CH, CH2N3, CH2NH2, CH2OAc, CH NPh)

Singh, Nem; Metla, Bhanu Prakasa Rao; Elias, Anil J.

doi:10.1016/j.jorganchem.2012.07.023

Cited by 10 publications

(5 citation statements)

References 46 publications

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“…All solvents were freshly distilled and used. Ferrocenecarboxylic acid, ferrocenecarboxamide, ferrocenylmethylamine, the sodium salt of carbomethoxycyclopentadiene, and tris(triphenylphosphine)cobalt chloride, as well as carboxylic acid, carboxamide, and aminomethyl derivatives of [η 5 -C 5 H 4 ]Co(η 4 -C 4 Ph 4 ) were prepared according to literature procedures. ,, Dimethyl carbonate, triphenylphosphine, oxalyl chloride (Spectrochem), picolinic acid, palladium acetate (Alfa Aesar), iodoarenes, and iodoalkenes were used as received. 1 H and 13 C NMR spectra were recorded on a Bruker Spectrospin DPX-300 NMR spectrometer at 300 and 75.47 MHz, respectively.…”

Section: Methodsmentioning

confidence: 99%

Picolinamide as a Directing Group on Metal Sandwich Compounds: sp² C–H Bond Activation and sp³ C–H Bond Oxidation

et al. 2017

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Palladium catalyzed bis-arylations, -alkylations, and -allylations on the Cp ring of iron and cobalt sandwich compounds have been achieved using the bidentate picolinamide directing group. This directing group along with catalytic Pd(OAc)2 was found to be highly efficient for C–H functionalization, giving up to 87% yields. The palladacyclic intermediate for the C–H activation of the Cp ring has been isolated and structurally characterized for the cobalt sandwich compound [η5-C5H5]Co(η4-C4Ph4). Attempted C–H annulation reactions using picolinamide-derived sandwich compounds did not yield the expected annulated products and instead oxidized the Cp- and picolinamide-bound CH2 unit to aldehydes. Detailed studies on this novel and unprecedented oxidation indicated that this happens only with the assistance of the picolinamide directing group. We have also shown that the sp2 C–H functionalization and the sp3 C–H oxidation can be effectively carried out as a one-pot reaction.

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Section: Methodsmentioning

confidence: 99%

Picolinamide as a Directing Group on Metal Sandwich Compounds: sp² C–H Bond Activation and sp³ C–H Bond Oxidation

et al. 2017

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“…Homogenous complex (6) was obtained as per the modified procedure described in the literature [34][35][36] with multistep route as shown in Scheme 1. The 1 H NMR spectrum of synthesized complex showed broad signal around 5.17 ppm which is characteristic of amide functional group along with other signal typical of complex 6 (as shown in Scheme 1).…”

Section: Resultsmentioning

confidence: 99%

“…S2 ) showed peaks around 7, 27, and 44 which are correspond to different aliphatic functionalities arising from the siloxane functional group [34,39]. The peak appears around 165 ppm corresponds to the carbonyl functionality, further, the broad peaks present around 72 and 113-123 ppm characteristic of (C 4 Ph 4 ) and phenyl group respectively [34,39]. The solid state NMR studies reveal that the successful grafting and the structural stability of the complex 6 on the surface of SBA-15 after heterogenization (Fig.…”

Section: Resultsmentioning

confidence: 99%

“…Chlorotris(triphenylphosphine)cobalt and sodium carbomethoxycyclopentadienide (2) were prepared as per the procedure described in literature [34][35][36] Ester functional group of compound 3, was hydrolysis using ethanolic potassium hydroxide solution to give rise to the corresponding acid (4) [34]. The resultant acid was extracted in ether (3 times, 30 ml) and dried.…”

Section: Solvents and General Proceduresmentioning

confidence: 99%

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Synthesis and Heterogenization of Siloxane Functionalized Cobalt Complex: Potential Catalyst for Oxidation of Alcohols

et al. 2015

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Cobalticinium complex containing siloxane moiety on ligand center was first time synthesized, characterized and heterogenized on the surface of SBA-15 molecular sieves. FT-IR and 29 Si-MAS-NMR spectrum evidence the successful grafting of the cobalt complex on the surface of SBA-15. N 2 sorption isotherm of cobalticinium complex grafted sample showed the decrease in surface area, pore volume, further confirms the presence of complex inside the channel of mesoporous SBA-15. The heterogenized complex exhibited promising activity for oxidation of alcohols with good selectivity of ketone. Further the catalytic activity remains intact after two recycles. Graphical Abstract Cobalticinium complex possessing siloxane functionality was prepared first time and heterogenized on SBA-15 surface. The resultant materials showed as promising recyclable heterogeneous catalyst for oxidation of alcohols.

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“…Over the decades, advances in synthetic chemistry resulted in the preparation of various polymerizable sandwich complexes in addition to ferrocene. Indeed, polymers containing sandwich complexes of hafnium, zirconium, vanadium, chromium, cobalt, titanium, and ruthenium have been reported.…”

Section: Sandwich Complexes As Monomers: Historical Context Researchmentioning

confidence: 99%

Sandwich Complex‐Containing Macromolecules: Property Tunability Through Versatile Synthesis

Abd‐El‐Aziz

Agatemor

Etkin

2014

Macromol. Rapid Commun.

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Sandwich complexes feature unique properties as the physical and electronic properties of a hydrocarbon ligand or its derivative are integrated into the physical, electronic, magnetic, and optical properties of a metal. Incorporation of these complexes into macromolecules results in intriguing physical, electrical, and optical properties that were hitherto unknown in organic-based macromolecules. These properties are tunable through well-designed synthetic strategies. This review surveys many of the synthetic approaches that have resulted in tuning the properties of sandwich complex-containing macromolecules. While the past two decades have seen an ever-growing number of research publications in this field, gaps remain to be filled. Thus, we expect this review to stimulate research interest towards bridging these gaps, which include the insolubility of some of these macromolecules as well as expanding the scope of the sandwich complexes.

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Synthesis and reactions of new 1,2- and 1,3-cyclopentadienyl disubstituted cobalt sandwich compounds (η5-C5H3R2)Co(η4-C4Ph4) (R CH2OH, CHO, C CH, CH2N3, CH2NH2, CH2OAc, CH NPh)

Cited by 10 publications

References 46 publications

Picolinamide as a Directing Group on Metal Sandwich Compounds: sp² C–H Bond Activation and sp³ C–H Bond Oxidation

Picolinamide as a Directing Group on Metal Sandwich Compounds: sp² C–H Bond Activation and sp³ C–H Bond Oxidation

Synthesis and Heterogenization of Siloxane Functionalized Cobalt Complex: Potential Catalyst for Oxidation of Alcohols

Sandwich Complex‐Containing Macromolecules: Property Tunability Through Versatile Synthesis

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Synthesis and reactions of new 1,2- and 1,3-cyclopentadienyl disubstituted cobalt sandwich compounds (η5-C5H3R2)Co(η4-C4Ph4) (R CH2OH, CHO, C CH, CH2N3, CH2NH2, CH2OAc, CH NPh)

Cited by 10 publications

References 46 publications

Picolinamide as a Directing Group on Metal Sandwich Compounds: sp2 C–H Bond Activation and sp3 C–H Bond Oxidation

Picolinamide as a Directing Group on Metal Sandwich Compounds: sp2 C–H Bond Activation and sp3 C–H Bond Oxidation

Synthesis and Heterogenization of Siloxane Functionalized Cobalt Complex: Potential Catalyst for Oxidation of Alcohols

Sandwich Complex‐Containing Macromolecules: Property Tunability Through Versatile Synthesis

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Picolinamide as a Directing Group on Metal Sandwich Compounds: sp² C–H Bond Activation and sp³ C–H Bond Oxidation

Picolinamide as a Directing Group on Metal Sandwich Compounds: sp² C–H Bond Activation and sp³ C–H Bond Oxidation