59487-11-5Relevant articles and documents
Rational Development of Cobalt β-Ketoiminate Complexes: Alternative Precursors for Vapor-Phase Deposition of Spinel Cobalt Oxide Photoelectrodes
Junge Puring, Kai,Zywitzki, Dennis,Taffa, Dereje H.,Rogalla, Detlef,Winter, Manuela,Wark, Michael,Devi, Anjana
, p. 5133 - 5144 (2018)
A series of six cobalt ketoiminates, of which one was previously reported but not explored as a chemical vapor deposition (CVD) precursor, namely, bis(4-(isopropylamino)pent-3-en-2-onato)cobalt(II) ([Co(ipki)2], 1), bis(4-(2-methoxyethylamino)pent-3-en-2-onato)cobalt(II) ([Co(meki)2], 2), bis(4-(2-ethoxyethylamino)pent-3-en-2-onato)cobalt(II) ([Co(eeki)2], 3), bis(4-(3-methoxy-propylamino)pent-3-en-2-onato)cobalt(II) ([Co(mpki)2], 4), bis(4-(3-ethoxypropylamino)pent-3-en-2-onato)cobalt(II) ([Co(epki)2], 5), and bis(4-(3-isopropoxypropylamino)pent-3-en-2-onato)cobalt(II) ([Co(ippki)2], 6) were synthesized and thoroughly characterized. Single-crystal X-ray diffraction (XRD) studies on compounds 1-3 revealed a monomeric structure with distorted tetrahedral coordination geometry. Owing to the promising thermal properties, metalorganic CVD of CoOx was performed using compound 1 as a representative example. The thin films deposited on Si(100) consisted of the spinel-phase Co3O4 evidenced by XRD, Rutherford backscattering spectrometry/nuclear reaction analysis, and X-ray photoelectron spectroscopy. Photoelectrochemical water-splitting capabilities of spinel CoOx films grown on fluorine-doped tin oxide (FTO) and TiO2-coated FTO revealed that the films show p-type behavior with conduction band edge being estimated to -0.9 V versus reversible hydrogen electrode. With a thin TiO2 underlayer, the CoOx films exhibit photocurrents related to proton reduction under visible light.
Synthetic and structural studies of ethyl zinc β-amidoenoates and β-ketoiminates
Bhide, Malavika A.,Carmalt, Claire J.,Knapp, Caroline E.,Manzi, Joe A.
, (2021)
A set of heteroleptic ethyl zinc β-amidoenoates (1, 2) and β-ketoiminates (3) of the form [LZnEt]2 with varying steric bulk have been synthesised via the reaction of diethylzinc with β-aminoenoate ligands HL1 and HL2 and β-ketoimine HL3. These complexes have been characterised via1 H and13 C NMR, mass spectrometry and single-crystal X-ray diffraction, which unambigu-ously determined all three structures as dimeric species in the solid state. We observe the unusual dimerisation of 1 and 2 through coordination of the central zinc atom to the methine carbon of the second monomer, which gives these complexes high reactivity. The thermal properties of complex 3 are explored via thermal gravimetric analysis (TGA), to investigate their potential as single-source precursors to zinc oxide, which shows that 3 has a significantly lower decomposition temperature as compared to its bis-ligated counterpart [Zn(L3)2 ], which gives 3 promise as a single-source precursor to zinc oxide.
Metal β-diketoiminate precursor use in aerosol assisted chemical vapour deposition of gallium- and aluminium-doped zinc oxide
Knapp, Caroline E.,Dyer, Caragh,Chadwick, Nicholas P.,Hazael, Rachael,Carmalt, Claire J.
, p. 35 - 41 (2018)
Aerosol assisted chemical vapour deposition (AACVD) has been used to deposit thin films of ZnO from the single-source precursor [Zn(OC(Me)CHC(Me)N(iPr))2] (1) affording highly transparent (>80%) and conductive films (sheet resistance ～70 KΩ/sq). Extension of this AACVD method whereby related precursors of the type, [R2M(OC(Me)CHC(Me)N(iPr))] (R = Et, M = Al (2); R = Me, M = Ga (3)), isolated as oils, were added to the precursor solution allowed for the deposition of aluminium- and gallium-doped ZnO (AZO and GZO) films, respectively. Complexes 1–3 were characterised by elemental analysis, NMR and mass spectrometry. Films were deposited in under 30 min at 400 °C, from CH2Cl2/toluene solutions with a N2 carrier gas. Herein we report the bulk resistivity, ρ, of AZO (0.252 Ω cm) and GZO (0.756 Ω cm) films deposited from this novel approach. All the films transparency exceeded 80% in the visible, X-ray diffraction (XRD) showed all films to crystallise in the wurtzite phase whilst X-ray photoemission spectroscopy (XPS) confirmed the presence of the Al and Ga dopants in the films, and highlighted the low C-contamination (a mechanism analogous to the Kirkendall effect confirmed that heating of GZO films at 1000 °C produced the spinel structure GaZn2O4.
Dinuclear cobalt complexes supported by biphenol and binaphthol-derived bis(salicylaldimine) ligands: synthesis, characterization and catalytic application in β-enaminone synthesis from 1,3-dicarbonyl compounds and aliphatic amines
Filkale, Adelew Estifanos,Pathak, Chandni
supporting information, p. 15109 - 15121 (2020/09/23)
Two new tetradentate ligands, namely, 3,3′-bis[((2,4,6-trimethyl-phenyl)imino)methyl]-[1,1′]-biphenyl-2,2′-diol,H2L1(1), and 3,3′-bis[((2,4,6-trimethylphenyl)imino)methyl]-[1,1′]-binaphthalenyl-2,2′-diol,H2L2(3), based on 2,2′-biphenol and 2,2′-binaphthol frameworks have been synthesized and characterized. Correspondingly, dinuclear cobalt complexes {Co[3,3′-bis-((R)-iminomethyl)-(1,1′)-biphenyl-2,2′-dioxo]}2(2) and {Co[3,3′-bis-((R)-iminomethyl)-(1,1′)-binaphthalenyl-2,2′-dioxo]}2(4) (where R = 2,4,6-Me3C6H2) were synthesizedviareactions of the respective ligands with tetrahydrate cobalt acetate. The complexes were then characterized by elemental analysis, mass spectrometry, IR, UV-vis, magnetic susceptibility and single-crystal X-ray diffraction analysis. The single-crystal X-ray crystallographic study indicates a distorted tetrahedral geometry for each of the metal ions in2and4. The magnetic susceptibility measurements at varying temperatures (5-300 K) showed that the complexes exhibit weak antiferromagnetic (AF) interactions. Both metal complexes2and4successfully catalysed the synthesis of β-enaminones from 1,3-dicarbonyl compounds and aliphatic amines under ambient conditions.
PROCESS FOR THE GENERATION OF METAL- OR SEMIMETAL-CONTAINING FILMS
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Page/Page column 28, (2020/12/29)
The present invention is in the field of processes for preparing inorganic metal- or semimetal- containing films. The process comprising (a) depositing a metal- or semimetal-containing compound from the gaseous state onto a solid substrate and (b) bringing the solid substrate in contact with a compound of general formula (I), (II), (III), (IV), (V), (VI), or (VII) in the gaseous state (I) (II) (III) (IV).. (V) (VI) (VII) wherein A is NR or O, E is CR'', CNR''2, N, PR''2, or SOR'', G is CR' or N, R is an alkyl group, an alkenyl group, an aryl group, or a silyl group and R' and R'' are hydrogen, an alkyl group, an alkenyl group, an aryl group, or a silyl group.
Electrochemical behaviour of amino substituted β-amino α,β-unsaturated ketones: A computational chemistry and experimental study
Ngake, Tankiso Lawrence,Potgieter, Johannes Hermanus,Conradie, Jeanet
, p. 1070 - 1082 (2019/01/05)
The synthesis, identification and electrochemical properties are reported here, for a series of five novel and seven known amino substituted β-amino α,β-unsaturated ketones (bidentate N,O-ligands) of the type CH3COCHC(NHR)CH3, where R = H, Ph, CH2Ph, CH(CH3)2, p-CF3-Ph or p-tBu-Ph (Series 1), as well as type PhCOCHC(NHR)CH3, where R = H, Ph, p-NO2-Ph, 3,5-di-Cl-Ph, 2-CF3-4-Cl-Ph, and also PhCOCHC(NHPh)CF3 (Series 2). The cyclic voltammograms measured in CH3CN, generally exhibit both a chemically and electrochemically irreversible reduction peak between ?1.2 V and ?3.1 V vs FcH/FcH+, producing an unstable radical anion, for most of these 1,3-amino ketones. Only ligands PhCOCHC(NHPh)CH3, PhCOCHC(NHPh)CF3 and PhCOCHC(NH(p-NO2-Ph))CH3, showed reversible electrochemical behaviour, at higher scan rates. Density functional theory (DFT) calculations proved the unpaired spin density in the radical anion to be distributed over the pseudo-aromatic O–C–C–C–N backbone of the 1,3-amino ketones, extending further over the phenyl rings of the phenyl-containing ligands. Various DFT calculated energies, such as the energy of the lowest unoccupied molecular orbital (the orbital into which the electron is added upon reduction), as well as the DFT calculated gas phase adiabatic electron affinities, relate linearly to the experimentally measured reduction potential. These obtained linear relationships confirmed that good communication via conjugation exists, between the R substituent on the amino group and the rest of the 1,3-amino ketone.
Redox Property of Enamines
Li, Yao,Wang, Dehong,Zhang, Long,Luo, Sanzhong
, p. 12071 - 12090 (2019/10/11)
Enamines are electron-rich compounds bearing intriguing redox properties. Herein, a series of secondary enamines condensed from primary amine and β-ketocarbonyls were synthesized and their electrochemical oxidation properties were systematically studied by cyclic voltammetry. Furthermore, theoretical calculation of oxidation potentials of enamines, particularly those catalytic intermediates, was also conducted to further broaden the scope investigated. Possible structural factors on oxidation and the nature of the resulted radical cation intermediates were revealed and discussed. Correlation of redox potentials with molecular properties such as highest occupied molecular orbital energies and natural population analysis charge were explored, and there appears no simple linear correlation. On the other hand, a good correlation with Mayr's nucleophilicity parameter N was noted among a range of catalytically relevant enamines. Spin population analysis disclosed that enamine radical cations mainly exhibit the carbon-center free radical feature. Taking experimental and computation data together, a comprehensive picture about the redox property of enamines is presented, which would provide guidance in the development of oxidative enamine catalysis and transformations.
β-Enaminone Synthesis from 1,3-Dicarbonyl Compounds and Aliphatic and Aromatic Amines Catalyzed by Iron Complexes of Fused Bicyclic Imidazo[1,5-a]pyridine Derived N-Heterocyclic Carbenes
Prakasham,Gangwar, Manoj Kumar,Ghosh, Prasenjit
, p. 295 - 313 (2019/01/24)
A series of Fe–NHC complexes (1–2)c of the fused bicyclic imidazo[1,5-a]pyridine framework of the type [CpFe(2-R-imidazo[1,5-a]pyridin-3-ylidene)(CO)2]BF4 {R = mesityl (1c), nPr (2c)} successfully carried out the synthesis of β-enamino ketones (3–10) and (17–27) and β-enamino esters (11–16) and (28–36) by the condensation of acyclic and cyclic 1,3-dicarbonyl compounds and various aliphatic and aromatic amines in the presence of light irradiation. Quite significantly, the catalytically relevant substrate adduct species of the type [CpFe(NHC)(acac)] (2e) and the product adduct species of the type [CpFe(NHC)(β-enaminone)] (2f) of the Fe–NHC precatalyst (2c) have been detected by mass spectrometry study. The [CpFe(2-R-imidazo[1,5-a]pyridin-3-ylidene)(CO)2]BF4 {R = mesityl (1c), nPr (2c)} complexes were obtained from their respective N–heterocyclic carbene precursors namely, the 2-R-imidazo[1,5-a]pyridin-2-ium chloride {R = mesityl (1a), nPr (2a)} by the reaction with CpFe(CO)2I in the presence of KN(SiMe3)2 followed by the salt metathesis reaction with AgBF4.
Synthesis, Characterization, and Thermal Properties of N -alkyl β-Diketiminate Manganese Complexes
Stalzer, Madelyn M.,Lohr, Tracy L.,Marks, Tobin J.
supporting information, p. 3017 - 3024 (2018/03/25)
A series of N,N′-dialkyl-β-diketiminato manganese(II) complexes was synthesized and characterized by single crystal X-ray diffraction, UV-vis and FTIR spectroscopy, and then assayed for volatility, thermal stability, and surface reactivity relevant to vap
Bimetallic Ag-Cu alloy nanoparticles as a highly active catalyst for the enamination of 1,3-dicarbonyl compounds
Rout, Lipeeka,Kumar, Aniket,Dhaka, Rajendra S.,Dash, Priyabrat
, p. 49923 - 49940 (2016/06/15)
Bimetallic nanoparticles, particularly those based on copper, have recently attracted a great deal of attention for the development of low cost and highly active catalysts due to the synergistic interaction between individual metal components. In this work, bimetallic Ag-Cu alloy nanoparticles were explored as a highly active and reusable catalyst for the enamination of 1,3-dicarbonyls using diverse amines. The nanocatalysts were intensively characterized by ultraviolet-visible (UV-Vis) spectroscopy, X-ray diffraction (XRD), high-resolution transmission electron microscopy-energy-dispersive spectroscopy (HRTEM-EDS) and valence band and core level X-ray photoelectron spectroscopy (XPS) to study the effect of the bimetallic structure and composition. In comparison to monometallic Ag and Cu nanoparticles, the alloyed Ag-Cu nanoparticles showed a high catalytic performance and the resultant catalytic activity was dependant on the Ag to Cu ratio. This enhanced catalytic activity should be related to the electronic interaction between Ag and Cu nanoparticles formed due to the intimate contact between them. Our study may serve as a foundation for designing efficient alloyed nanocatalysts for fine chemical synthesis via enamination reactions.
