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Inorganics, Volume 5, Issue 4 (December 2017)

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Cover Story (view full-size image) Three dinuclear Fe(II) triple helicates incorporating the different conformation were obtained and [...] Read more.
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Open AccessArticle The Silacyclobutene Ring: An Indicator of Triplet State Baird-Aromaticity
Received: 23 October 2017 / Revised: 8 December 2017 / Accepted: 11 December 2017 / Published: 15 December 2017
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Abstract
Baird’s rule tells that the electron counts for aromaticity and antiaromaticity in the first ππ* triplet and singlet excited states (T1 and S1) are opposite to those in the ground state (S0). Our hypothesis is that a silacyclobutene
[...] Read more.
Baird’s rule tells that the electron counts for aromaticity and antiaromaticity in the first ππ* triplet and singlet excited states (T1 and S1) are opposite to those in the ground state (S0). Our hypothesis is that a silacyclobutene (SCB) ring fused with a [4n]annulene will remain closed in the T1 state so as to retain T1 aromaticity of the annulene while it will ring-open when fused to a [4n + 2]annulene in order to alleviate T1 antiaromaticity. This feature should allow the SCB ring to function as an indicator for triplet state aromaticity. Quantum chemical calculations of energy and (anti)aromaticity changes along the reaction paths in the T1 state support our hypothesis. The SCB ring should indicate T1 aromaticity of [4n]annulenes by being photoinert except when fused to cyclobutadiene, where it ring-opens due to ring-strain relief. Full article
(This article belongs to the Special Issue Coordination Chemistry of Silicon)
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Open AccessArticle Field-Induced Single-Ion Magnet Behaviour in Two New Cobalt(II) Coordination Polymers with 2,4,6-Tris(4-pyridyl)-1,3,5-triazine
Received: 28 November 2017 / Revised: 10 December 2017 / Accepted: 11 December 2017 / Published: 15 December 2017
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Abstract
We herein reported the syntheses, crystal structures, and magnetic properties of a two-dimensional coordination polymer {[CoII(TPT)2/3(H2O)4][CH3COO]2·(H2O)4}n (1) and a chain compound {[CoII(TPT)
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We herein reported the syntheses, crystal structures, and magnetic properties of a two-dimensional coordination polymer {[CoII(TPT)2/3(H2O)4][CH3COO]2·(H2O)4}n (1) and a chain compound {[CoII(TPT)2(CHOO)2(H2O)2]}n (2) based on the 2,4,6-Tris(4-pyridyl)-1,3,5-triazine (TPT) ligand. Structure analyses showed that complex 1 had a cationic hexagonal framework structure, while 2 was a neutral zig-zag chain structure with different distorted octahedral coordination environments. Magnetic measurements revealed that both complexes exhibit large easy-plane magnetic anisotropy with the zero-field splitting parameter D = 47.7 and 62.1 cm−1 for 1 and 2, respectively. This magnetic anisotropy leads to the field-induced slow magnetic relaxation behaviour. However, their magnetic dynamics are quite different; while complex 1 experienced a dominating thermally activated Orbach relaxation at the whole measured temperature region, 2 exhibited multiple relaxation pathways involving direct, Raman, and quantum tunneling (QTM) processes at low temperatures and Orbach relaxation at high temperatures. The present complexes enlarge the family of framework-based single-ion magnets (SIMs) and highlight the significance of the structural dimensionality to the final magnetic properties. Full article
(This article belongs to the Special Issue Single-Molecule Magnets)
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Open AccessArticle Lewis Base Complexes of Magnesium Borohydride: Enhanced Kinetics and Product Selectivity upon Hydrogen Release
Received: 3 November 2017 / Revised: 27 November 2017 / Accepted: 28 November 2017 / Published: 6 December 2017
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Abstract
Tetrahydofuran (THF) complexed to magnesium borohydride has been found to have a positive effect on both the reactivity and selectivity, enabling release of H2 at <200 °C and forms Mg(B10H10) with high selectivity. Full article
(This article belongs to the Special Issue Functional Materials Based on Metal Hydrides)
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Open AccessArticle Molecular Structures of Enantiomerically-Pure (S)-2-(Triphenylsilyl)- and (S)-2-(Methyldiphenylsilyl)pyrrolidinium Salts
Received: 31 October 2017 / Revised: 1 December 2017 / Accepted: 2 December 2017 / Published: 6 December 2017
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Abstract
Silyl-substituted pyrrolidines have gained increased interest for the design of new catalyst scaffolds. The molecular structures of four enantiomerically-pure 2-silylpyrrolidinium salts are reported. The perchlorate salts of (S)-2-(triphenylsilyl)pyrrolidine [(S)-1·HClO4] and (S)-2-(methyldiphenylsilyl)pyrrolidine [(S
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Silyl-substituted pyrrolidines have gained increased interest for the design of new catalyst scaffolds. The molecular structures of four enantiomerically-pure 2-silylpyrrolidinium salts are reported. The perchlorate salts of (S)-2-(triphenylsilyl)pyrrolidine [(S)-1·HClO4] and (S)-2-(methyldiphenylsilyl)pyrrolidine [(S)-2·HClO4], the trifluoroacetate (S)-2·TFA, and the methanol-including hydrochloride (S)-1·HCl·MeOH were elucidated by X-ray crystallography and discussed in terms of hydrogen-bond interactions. Full article
(This article belongs to the Special Issue Coordination Chemistry of Silicon)
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Open AccessArticle The Mechanism of Rh-Catalyzed Transformation of Fatty Acids to Linear Alpha olefins
Received: 15 October 2017 / Revised: 23 November 2017 / Accepted: 29 November 2017 / Published: 4 December 2017
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Abstract
Linear alpha olefins (LAOs) are key commodity chemicals and petrochemical intermediates that are currently produced from fossil resources. Fatty acids are the obvious renewable starting material for LAOs, which can be obtained via transition-metal-catalyzed decarbonylative dehydration. However, even the best catalysts that have
[...] Read more.
Linear alpha olefins (LAOs) are key commodity chemicals and petrochemical intermediates that are currently produced from fossil resources. Fatty acids are the obvious renewable starting material for LAOs, which can be obtained via transition-metal-catalyzed decarbonylative dehydration. However, even the best catalysts that have been obtained to date, which are based on palladium, are not active and stable enough for industrial use. To provide insight for design of better catalysts, we here present the first computationally derived mechanism for another attractive transition-metal for this reaction, rhodium. By comparing the calculated mechanisms and free energy profiles for the two metals, Pd and Rh, we single out important factors for a facile, low-barrier reaction and for a stable catalyst. While the olefin formation is rate limiting for both of the metals, the rate-determining intermediate for Rh is, in contrast to Pd, the starting complex, (PPh3)2Rh(CO)Cl. This complex largely draws its stability from the strength of the Rh(I)–CO bond. CO is a much less suitable ligand for the high-oxidation state Rh(III). However, for steric reasons, rhodium dissociates a bulkier triphenylphosphine and keeps the carbonyl during the oxidative addition, which is less favorable than for Pd. When compared to Pd, which dissociates two phosphine ligands at the start of the reaction, the catalytic activity of Rh also appears to be hampered by its preference for high coordination numbers. The remaining ancillary ligands leave less space for the metal to mediate the reaction. Full article
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Open AccessArticle Microstructure and Hydrogen Storage Properties of Ti1V0.9Cr1.1 Alloy with Addition of x wt % Zr (x = 0, 2, 4, 8, and 12)
Received: 4 October 2017 / Revised: 28 November 2017 / Accepted: 28 November 2017 / Published: 3 December 2017
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Abstract
The effect of adding Zr on microstructure and hydrogen storage properties of BCC Ti1V0.9Cr1.1 synthesized by arc melting was studied. The microstructures of samples with Zr were multiphase with a main BCC phase and secondary Laves phases C15
[...] Read more.
The effect of adding Zr on microstructure and hydrogen storage properties of BCC Ti1V0.9Cr1.1 synthesized by arc melting was studied. The microstructures of samples with Zr were multiphase with a main BCC phase and secondary Laves phases C15 and C14. The abundance of secondary phases increased with increasing amount of zirconium. We found that addition of Zr greatly enhanced the first hydrogenation kinetics. The addition of 4 wt % of Zr produced fast kinetics and high hydrogen storage capacity. Addition of higher amount of Zr had for effect of decreasing the hydrogen capacity. The reduction in hydrogen capacity might be due to the increased secondary phase abundance. The effect of air exposure was also studied. It was found that, for the sample with 12 wt % of Zr, exposure to the air resulted in appearance of an incubation time in the first hydrogenation and a slight reduction of hydrogen capacity. Full article
(This article belongs to the Special Issue Functional Materials Based on Metal Hydrides)
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Open AccessArticle Reactivity of Zinc Halide Complexes Containing Camphor-Derived Guanidine Ligands with Technical rac-Lactide
Received: 27 October 2017 / Revised: 21 November 2017 / Accepted: 23 November 2017 / Published: 30 November 2017
Cited by 2 | PDF Full-text (3942 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Three new zinc complexes with monoamine–guanidine hybridligands have been prepared, characterized by X-ray crystallography and NMR spectroscopy, and tested in the solvent-free ring-opening polymerization of rac-lactide. Initially the ligands were synthesized from camphoric acid to obtain TMGca and DMEGca and then reacted
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Three new zinc complexes with monoamine–guanidine hybridligands have been prepared, characterized by X-ray crystallography and NMR spectroscopy, and tested in the solvent-free ring-opening polymerization of rac-lactide. Initially the ligands were synthesized from camphoric acid to obtain TMGca and DMEGca and then reacted with zinc(II) halides to form zinc complexes. All complexes have a distorted tetrahedral coordination. They were utilized as catalysts in the solvent-free polymerization of technical rac-lactide at 150 °C. Colorless polylactide (PLA) can be produced and after 2 h conversion up to 60% was reached. Furthermore, one zinc chlorido complex was tested with different qualities of lactide (technical and recrystallized) and with/without the addition of benzyl alcohol as a co-initiator. The kinetics were monitored by in situ FT-IR or 1H NMR spectroscopy. All kinetic measurements show first-order behavior with respect to lactide. The influence of the chiral complexes on the stereocontrol of PLA was examined. Moreover, with MALDI-ToF measurements the end-group of the obtained polymer was determined. DFT and NBO calculations give further insight into the coordination properties. All in all, these systems are robust against impurities and water in the lactide monomer and show great catalytic activity in the ROP of lactide. Full article
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Open AccessCommunication Construction of a Planar Tetrapalladium Cluster by the Reaction of Palladium(0) Bis(isocyanide) with Cyclic Tetrasilane
Received: 6 November 2017 / Revised: 18 November 2017 / Accepted: 22 November 2017 / Published: 27 November 2017
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Abstract
The planar tetrapalladium cluster Pd4{Si(iPr)2}3(CNtBu)4 (4) was synthesised in 86% isolated yield by the reaction of palladium(0) bis(isocyanide) Pd(CNtBu)2 with octaisopropylcyclotetrasilane (3). In the course
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The planar tetrapalladium cluster Pd4{Si(iPr)2}3(CNtBu)4 (4) was synthesised in 86% isolated yield by the reaction of palladium(0) bis(isocyanide) Pd(CNtBu)2 with octaisopropylcyclotetrasilane (3). In the course of this reaction, the palladium atoms are clustered via insertion into the Si–Si bonds of 3, followed by extrusion of one SiiPr2 moiety and reorganisation to afford 4 with a 54-electron configuration. The CNtBu ligand in 4 was found to be easily replaced by N-heterocyclic carbene (iPr2IMMe) to afford the more coordinatively unsaturated cluster Pd4{Si(iPr)2}3(iPr2IMMe)3 (5) having the planar Pd4Si3 core. On the other hand, the replacement of CNtBu with a sterically compact ligand trimethylolpropane phosphite {P(OCH2)3CEt} led to a planar tripalladium cluster Pd3{Si(iPr)2}3{P(OCH2)3CEt}3 (6) and Pd{P(OCH2)3CEt}4 in 1:1 molar ratio as products. Full article
(This article belongs to the Special Issue Coordination Chemistry of Silicon)
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Open AccessArticle Investigation of the Reversible Lithiation of an Oxide Free Aluminum Anode by a LiBH4 Solid State Electrolyte
Received: 19 September 2017 / Revised: 21 November 2017 / Accepted: 21 November 2017 / Published: 23 November 2017
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Abstract
In this study, we analyze and compare the physical and electrochemical properties of an all solid-state cell utilizing LiBH4 as the electrolyte and aluminum as the active anode material. The system was characterized by galvanostatic lithiation/delithiation, cyclic voltammetry (CV), X-ray diffraction (XRD), energy
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In this study, we analyze and compare the physical and electrochemical properties of an all solid-state cell utilizing LiBH4 as the electrolyte and aluminum as the active anode material. The system was characterized by galvanostatic lithiation/delithiation, cyclic voltammetry (CV), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), Raman spectroscopy, electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM). Constant current cycling demonstrated that the aluminum anode can be reversibly lithiated over multiple cycles utilizing a solid-state electrolyte. An initial capacity of 895 mAh/g was observed and is close to the theoretical capacity of aluminum. Cyclic voltammetry of the cell was consistent with the constant current cycling data and showed that the reversible lithiation/delithiation of aluminum occurs at 0.32 V and 0.38 V (vs. Li+/Li) respectively. XRD of the aluminum anode in the initial and lithiated state clearly showed the formation of a LiAl (1:1) alloy. SEM-EDS was utilized to examine the morphological changes that occur within the electrode during cycling. This work is the first example of reversible lithiation of aluminum in a solid-state cell and further emphasizes the robust nature of the LiBH4 electrolyte. This demonstrates the possibility of utilizing other high capacity anode materials with a LiBH4 based solid electrolyte in all-solid-state batteries. Full article
(This article belongs to the Special Issue Functional Materials Based on Metal Hydrides)
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Open AccessArticle Dehydrogenation of Surface-Oxidized Mixtures of 2LiBH4 + Al/Additives (TiF3 or CeO2)
Received: 28 September 2017 / Revised: 9 November 2017 / Accepted: 16 November 2017 / Published: 21 November 2017
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Abstract
Research for suitable hydrogen storage materials is an important ongoing subject. LiBH4–Al mixtures could be attractive; however, several issues must be solved. Here, the dehydrogenation reactions of surface-oxidized 2LiBH4 + Al mixtures plus an additive (TiF3 or CeO2
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Research for suitable hydrogen storage materials is an important ongoing subject. LiBH4–Al mixtures could be attractive; however, several issues must be solved. Here, the dehydrogenation reactions of surface-oxidized 2LiBH4 + Al mixtures plus an additive (TiF3 or CeO2) at two different pressures are presented. The mixtures were produced by mechanical milling and handled under welding-grade argon. The dehydrogenation reactions were studied by means of temperature programmed desorption (TPD) at 400 °C and at 3 or 5 bar initial hydrogen pressure. The milled and dehydrogenated materials were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transformed infrared spectroscopy (FT-IR) The additives and the surface oxidation, promoted by the impurities in the welding-grade argon, induced a reduction in the dehydrogenation temperature and an increase in the reaction kinetics, as compared to pure (reported) LiBH4. The dehydrogenation reactions were observed to take place in two main steps, with onsets at 100 °C and 200–300 °C. The maximum released hydrogen was 9.3 wt % in the 2LiBH4 + Al/TiF3 material, and 7.9 wt % in the 2LiBH4 + Al/CeO2 material. Formation of CeB6 after dehydrogenation of 2LiBH4 + Al/CeO2 was confirmed. Full article
(This article belongs to the Special Issue Functional Materials Based on Metal Hydrides)
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Open AccessArticle Thermodynamic Properties and Reversible Hydrogenation of LiBH4–Mg2FeH6 Composite Materials
Received: 8 October 2017 / Revised: 2 November 2017 / Accepted: 2 November 2017 / Published: 16 November 2017
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Abstract
In previous studies, complex hydrides LiBH4 and Mg2FeH6 have been reported to undergo simultaneous dehydrogenation when ball-milled as composite materials (1 − x)LiBH4 + xMg2FeH6. The simultaneous hydrogen release led to a
[...] Read more.
In previous studies, complex hydrides LiBH4 and Mg2FeH6 have been reported to undergo simultaneous dehydrogenation when ball-milled as composite materials (1 − x)LiBH4 + xMg2FeH6. The simultaneous hydrogen release led to a decrease of the dehydrogenation temperature by as much as 150 K when compared to that of LiBH4. It also led to the modified dehydrogenation properties of Mg2FeH6. The simultaneous dehydrogenation behavior between stoichiometric ratios of LiBH4 and Mg2FeH6 is not yet understood. Therefore, in the present work, we used the molar ratio x = 0.25, 0.5, and 0.75, and studied the isothermal dehydrogenation processes via pressure–composition–isothermal (PCT) measurements. The results indicated that the same stoichiometric reaction occurred in all of these composite materials, and x = 0.5 was the molar ratio between LiBH4 and Mg2FeH6 in the reaction. Due to the optimal composition ratio, the composite material exhibited enhanced rehydrogenation and reversibility properties: the temperature and pressure of 673 K and 20 MPa of H2, respectively, for the full rehydrogenation of x = 0.5 composite, were much lower than those required for the partial rehydrogenation of LiBH4. Moreover, the x = 0.5 composite could be reversibly hydrogenated for more than four cycles without degradation of its H2 capacity. Full article
(This article belongs to the Special Issue Functional Materials Based on Metal Hydrides)
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Open AccessArticle Ruthenium-Catalyzed Dimerization of 1,1-Diphenylpropargyl Alcohol to a Hydroxybenzocyclobutene and Related Reactions
Received: 28 October 2017 / Revised: 14 November 2017 / Accepted: 14 November 2017 / Published: 16 November 2017
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Abstract
Propargyl alcohol is a useful synthon in synthetic organic chemistry. We found that the ruthenium(II) complex [Cp*RuCl(diene)] (Cp* = η5-C5Me5; diene = isoprene or 1,5-cyclooctadiene (cod)) catalyzes dimerization of 1,1-diphenylprop-2-yn-1-ol (1,1-diphenylpropargyl alcohol, 1a) at room temperature
[...] Read more.
Propargyl alcohol is a useful synthon in synthetic organic chemistry. We found that the ruthenium(II) complex [Cp*RuCl(diene)] (Cp* = η5-C5Me5; diene = isoprene or 1,5-cyclooctadiene (cod)) catalyzes dimerization of 1,1-diphenylprop-2-yn-1-ol (1,1-diphenylpropargyl alcohol, 1a) at room temperature to afford an alkylidenebenzocyclobutenyl alcohol 2a quantitatively. Meanwhile, a stoichiometric reaction of the related hydrido complex [Cp*RuH(cod)] with 1a at 50 °C led to isolation of a ruthenocene derivative 4 bearing a cyclopentadienyl ring generated by dehydrogenative trimerization of 1a. Detailed structures of 2a and 4 were determined by X-ray crystallography. The reaction mechanisms for the formation of 2a and 4 were proposed. Full article
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Open AccessArticle Synthesis of a Dichlorodigermasilane: Double Si–Cl Activation by a Ge=Ge Unit
Received: 21 October 2017 / Revised: 8 November 2017 / Accepted: 10 November 2017 / Published: 14 November 2017
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Abstract
Halogenated oligosilanes and oligogermanes are interesting compounds in oligosilane chemistry from the viewpoint of silicon-based-materials. Herein, it was demonstrated that a 1,2-digermacyclobutadiene derivative could work as a bis-germylene building block towards double Si–Cl activation to give a halogenated oligometallane, a bis(chlorogermyl)dichlorosilane derivative. Full article
(This article belongs to the Special Issue Coordination Chemistry of Silicon)
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Open AccessArticle Mechanistic Implications for the Ni(I)-Catalyzed Kumada Cross-Coupling Reaction
Received: 9 October 2017 / Revised: 7 November 2017 / Accepted: 10 November 2017 / Published: 14 November 2017
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Abstract
Herein we report on the cross-coupling reaction of phenylmagnesium bromide with aryl halides using the well-defined tetrahedral Ni(I) complex, [(Triphos)NiICl] (Triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane). In the presence of 0.5 mol % [(Triphos)NiICl], good to excellent yields (75–97%) of the respective
[...] Read more.
Herein we report on the cross-coupling reaction of phenylmagnesium bromide with aryl halides using the well-defined tetrahedral Ni(I) complex, [(Triphos)NiICl] (Triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane). In the presence of 0.5 mol % [(Triphos)NiICl], good to excellent yields (75–97%) of the respective coupling products within a reaction time of only 2.5 h at room temperature were achieved. Likewise, the tripodal Ni(II)complexes [(κ2-Triphos)NiIICl2] and [(κ3-Triphos)NiIICl](X) (X = ClO4, BF4) were tested as potential pre-catalysts for the Kumada cross-coupling reaction. While the Ni(II) complexes also afford the coupling products in comparable yields, mechanistic investigations by UV/Vis and electron paramagnetic resonance (EPR) spectroscopy indicate a Ni(I) intermediate as the catalytically active species in the Kumada cross-coupling reaction. Based on experimental findings and density functional theory (DFT) calculations, a plausible Ni(I)-catalyzed reaction mechanism for the Kumada cross-coupling reaction is presented. Full article
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Open AccessArticle Biodegradation of Cosmetics Products: A Computational Study of Cytochrome P450 Metabolism of Phthalates
Received: 10 October 2017 / Revised: 1 November 2017 / Accepted: 7 November 2017 / Published: 12 November 2017
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Abstract
Cytochrome P450s are a broad class of enzymes in the human body with important functions for human health, which include the metabolism and detoxification of compounds in the liver. Thus, in their catalytic cycle, the P450s form a high-valent iron(IV)-oxo heme cation radical
[...] Read more.
Cytochrome P450s are a broad class of enzymes in the human body with important functions for human health, which include the metabolism and detoxification of compounds in the liver. Thus, in their catalytic cycle, the P450s form a high-valent iron(IV)-oxo heme cation radical as the active species (called Compound I) that reacts with substrates through oxygen atom transfer. This work discusses the possible degradation mechanisms of phthalates by cytochrome P450s in the liver, through computational modelling, using 2-ethylhexyl-phthalate as a model substrate. Phthalates are a type of compound commonly found in the environment from cosmetics usage, but their biodegradation in the liver may lead to toxic metabolites. Experimental studies revealed a multitude of products and varying product distributions among P450 isozymes. To understand the regio- and chemoselectivity of phthalate activation by P450 isozymes, we focus here on the mechanisms of phthalate activation by Compound I leading to O-dealkylation, aliphatic hydroxylation and aromatic hydroxylation processes. We set up model complexes of Compound I with the substrate and investigated the reaction mechanisms for products using the density functional theory on models and did a molecular mechanics study on enzymatic structures. The work shows that several reaction barriers in the gas-phase are close in energy, leading to a mixture of products. However, when we tried to dock the substrate into a P450 isozyme, some of the channels were inaccessible due to unfavorable substrate positions. Product distributions are discussed under various reaction conditions and rationalized with valence bond and thermodynamic models. Full article
(This article belongs to the Special Issue Metal–Oxo Complexes)
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