Closing the loop: captured CO2 as a feedstock in the chemical industry

http://pubs.rsc.org/en/content/articlelanding/2015/ee/c5ee02591e#!divAbstract

Alexander Otto, Thomas Grube, Sebastian Schieben, and Detlef Stolten

Energy Environ. Sci. 2015, 8, 3283-3297

Abstract: The utilization of ‘captured’ CO₂ as a feedstock in the chemical industry for the synthesis of certain chemical products offers an option for preventing several million tons of CO₂ emissions each year while increasing independence from fossil fuels. For this reason, interest is increasing in the feasibility of deploying captured CO₂ in this manner. Numerous scientific publications describe laboratory experiments in which CO₂ has been successfully used as a feedstock for the synthesis of various chemical products. However, many of these publications have focused on the feasibility of syntheses without considering the ancillary benefits of CO₂ emissions reduction if the CO₂ is sourced from effluent or the potential profitability of this process. Evaluating these environmental and economic benefits is important for promoting the further development of benign CO₂ applications. Given the multitude of CO₂ utilization reactions in the laboratory context, an initial assessment must be undertaken to identify those which have the most potential for future technical exploration and development. To achieve this, 123 reactions from the literature were identified and evaluated with the help of selection criteria specifically developed for this project. These criteria incorporate both the quantitative potential of reducing CO₂ and possible economic benefits of these syntheses. The selected reactions are divided into bulk and fine chemicals. Of the bulk chemicals, formic acid, oxalic acid, formaldehyde, methanol, urea and dimethyl ether, and of the fine chemicals, methylurethane, 3-oxo-pentanedioic acid, 2-imidazolidinone, ethylurethane, 2-oxazolidone and isopropyl isocyanate, mostly fulfil the selection criteria in each category.

Kinetics and Mechanism of the Chlorate−Bromide Reaction

Kinetics and Mechanism of the Chlorate−Bromide Reaction

Rafaela T. P. Sant’Anna and Roberto B. Faria*

Instituto de Química, Universidade Federal do Rio de Janeiro, Av. Athos da Silveira Ramos 149, CT, Bloco A, 21941-611 Rio de Janeiro, RJ Brazil

Inorg. Chem. 2015, 54, 10415-10421.

http://pubs.acs.org/doi/pdf/10.1021/acs.inorgchem.5b01857

Abstract:
The chlorate−bromide reaction, ClO3 − + 6Br− + 6H+ → 3Br2 + Cl− + 3H2O, was followed at the Br3 −/Br2 isosbestic point (446 nm). A fifthorder rate law was found: 1 /3 d[Br2]/dt = k[ClO3 −][Br−][H+ ] 3 (k = 5.10 × 10−6 s −1 L4 mol−4 ) at 25 °C and I = 2.4 mol L−1 . At high bromide concentrations, the bromide order becomes close to zero, indicating a saturation profile on bromide concentration, similar to the chloride saturation profile observed in the chlorate−chloride reaction. A mechanism is proposed that considers the formation of the intermediate BrOClO2 2−, similar to the intermediate ClOClO2 2− proposed in the mechanism of the chlorate−chloride reaction.

TOC:

Influence of Elemental Iodine on Imidazolium-Based Ionic Liquids: Solution and Solid-State Effects

Influence of Elemental Iodine on Imidazolium-Based Ionic Liquids: Solution and Solid-State Effects

Zhaofu Fei, Felix D. Bobbink, Emilia Pa ́ unescu, Rosario Scopelliti, and Paul J. Dyson*

Institut des Sciences et Ingenierie Chimiques, Ecole Polytechnique Fe ́ dé rale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland

Inorg. Chem. 2015, 54, 10504-10512.

http://pubs.acs.org/doi/pdf/10.1021/acs.inorgchem.5b02021

Abstract:
Ionic liquids doped with I2, usually resulting in the formation of polyiodide anions, are extensively used as electrolytes and in iodination reactions. Herein, NMR spectroscopy and single-crystal X-ray diffraction were used to rationalize the structures of imidazolium-based polyiodide ionic liquids in the liquid and solid states. Combined, these studies show that extensive interactions between the imidazolium cation and the resulting polyiodide anion are present, which have the net effect of lengthening, polarizing, and weakening the I−I bonds in the anion. This bond weakening rationalizes the high conductivity and reactivity of ionic liquids doped with I2.

TOC:

From proton transferred to cyclometalated platinum(IV) complex: Crystal structure and biological activity

http://www.sciencedirect.com/science/article/pii/S0022328X1530125X

• Anita Abedi^a, 
• Vahid Amani^b, 
• Nasser Safari^b,, 
• S. Nasser Ostad^c, 
• Behrouz Notash^b

• ^a Department of Chemistry, North Tehran Branch, Islamic Azad University, Tehran 19585-936, Iran
• ^b Department of Chemistry, Shahid Beheshti University, G. C., Evin, Tehran 19839-63113, Iran
• ^c Department of Toxicology & Pharmacology, University of Tehran Medical Sciences, Tehran 14155-6451, Iran
• doi:10.1016/j.jorganchem.2015.08.023
• JOMC 2015, 800, 30-37
• 
  
• Abstract: 
A new proton transfer complex of [6,6′-dmbipy.H]₂[PtCl₆] (1) was prepared from the reaction of H₂PtCl₆.6H₂O with 6,6′-dimethyl-2,2'-bipyridine (6,6′-dmbipy) in CH₃CN at room temperature. The cyclometalated complex of mer-[Pt(6,6′-dmbipy-κ²N,C)Cl₃(DMF-κO)] (2) was prepared from the recrystallization of complex 1, in a mixture of DMF/DMSO/H₂O (6:2:1) at 60 °C, in which the first C–H bond activation in a bipyridine ring with Pt(IV) ion was observed. In vitro cytotoxicity against four cultures: NIH-3T3, Caco-2, HT-29 and T47D were studied using MTT assays. Interestingly, compound 2 is more potent in killing a colon cancer cell line than cisplatin, since it exhibits extensively less toxicity on normal cells. Both complexes were characterized by elemental analysis, FT-IR, ¹H NMR, UV–Vis spectra and X-ray crystallography.

Anti-Markovnikov Hydroamination of Homoallylic Amines

http://pubs.acs.org/doi/abs/10.1021/jacs.5b08500

Seth C. Ensign, Evan P. Vanable, Gregory D. Kortman, Lee J. Weir, and Kami L. Hull*

Department of Chemistry, University of Illinois at Urbana−Champaign, 600 South Mathews Avenue, Urbana, Illinois 61820, United States

J. Am. Chem. Soc., Article ASAP

DOI: 10.1021/jacs.5b08500

Publication Date (Web): October 12, 2015

Copyright © 2015 American Chemical Society

Abstract: The development of an anti-Markovnikov-selective hydroamination of unactivated alkenes is a significant challenge in organometallic chemistry. Herein, we present the rhodium-catalyzed anti-Markovnikov-selective hydroamination of homoallylic amines. The proximal Lewis basic amine serves to promote reactivity and enforce regioselectivity through the formation of the favored metallacycle, thus over-riding the inherent reactivity of the alkene. The scope of both the amine nucleophiles and homoallylic amines that participate in the reaction is demonstrated.

NHC Versus Pyridine: How “Teeth” Change the Redox Behavior of Iron(II) Complexes

http://pubs.acs.org/doi/10.1021/acs.organomet.5b00732


NHC Versus Pyridine: How “Teeth” Change the Redox Behavior of Iron(II) Complexes
Daniel T. Weiss†, Markus R. Anneser†, Stefan Haslinger†, Alexander Pöthig‡, Mirza Cokoja§, Jean-Marie Basset∥, and Fritz E. Kühn*†

† Chair of Inorganic Chemistry/Molecular Catalysis, Department of Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstraße 4, D-85747 Garching bei München, Germany
‡ Catalysis Research Center, Technische Universität München, Ernst-Otto-Fischer-Straße 1, D-85747 Garching bei München, Germany
§ Chair of Inorganic & Organometallic Chemistry, Department of Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstraße 4, D-85747 Garching bei München, Germany
∥ KAUST Catalysis Center, King Abdullah University of Science and Technology, Thuwal 23955-6900, Kingdom of Saudi Arabia
Organometallics, 2015, 34 (20), pp 5155–5166
DOI: 10.1021/acs.organomet.5b00732
Publication Date (Web): October 6, 2015








A series of octahedral iron(II) complexes with tetradentate NHC/pyridine hybrid ligands containing up to three pyridyl units was designed to study the influence of NHC and pyridine donors on the electronic structure of the metal center. Structural analysis of the iron complexes by NMR spectroscopy and single-crystal X-ray diffraction reveals different coordination modes of the ligand depending on the linkage of the different donor moieties. The oxidation potentials of all complexes correlate linearly with the number of NHC moieties coordinated to iron, as shown by cyclic voltammetry. The influence, although minor, of structural properties on the oxidation potential and (in one case) the influence of the oxidation state of the coordination geometry of the hybrid ligand are also demonstrated.

Synthesis and Characterization of New (η5-Cyclopentadienyl)dicarbonylruthenium(II) Amine Complexes: Their Application as Homogeneous Catalysts in Styrene Oxidation

http://pubs.acs.org/doi/10.1021/acs.organomet.5b00564



Synthesis and Characterization of New (η5-Cyclopentadienyl)dicarbonylruthenium(II) Amine Complexes: Their Application as Homogeneous Catalysts in Styrene Oxidation
Eunice A. Nyawade, Holger B. Friedrich*, Bernard Omondi, and Philani Mpungose

School of Chemistry and Physics, University of KwaZulu-Natal, Private Bag X54001, Durban 4000, South Africa
Organometallics, 2015, 34 (20), pp 4922–4931
DOI: 10.1021/acs.organomet.5b00564
Publication Date (Web): October 14, 2015







The water-soluble ruthenium(II) mononuclear complexes [CpRu(CO)2NH2R]BF4 (Cp = η5-C5H5; R = C6H11 (1), C6H5 (2), CH2C6H5 (3), CH(CH3)C6H5 (4), CH2(C6H4O)CH3 (5), CH2(C6H4)CN (6), C6H2(CH3)3 (7), CH2CHCH2 (8), CH(CH3)2 (9)) were synthesized from the reaction of the organometallic Lewis acid [CpRu(CO)2]BF4 with amine ligands at room temperature. These complexes are reported for the first time and have been fully characterized by IR, high-resolution mass spectrometry, 1H and 13C NMR spectroscopy, and elemental analysis. Spectral data show that the amines are σ-bonded to the metal center via the nitrogen atom. The crystal structures of complexes 3 and 8 were determined by single-crystal X-ray crystallography. The 4-methoxybenzylamine, 4-aminomethylbenzonitrile and allylamine groups preferentially bind to the metal center via the amine nitrogen. The ruthenium complexes 1, 3–6, 9, and [CpRu(CO)2NH2CH3]BF4 (10) and the dinuclear complex [CpRu(CO)2NH2(CH2)6NH2(CO)2-RuCp][BF4]2 (11) demonstrated excellent catalytic activity in the oxidation of styrene using NaIO4 as the co-oxidant with over 95% conversion and benzaldehyde yields, respectively, in some cases.