Orthocarbonic Acid Research Articles

Exploring the CO2 photocatalytic evolution onto the CuO (1 1 0) surface: A combined theoretical and experimental study

A combined theoretical and experimental study was performed to elucidate the photocatalytic potential of tenorite, CuO (1 1 0) and to assess the evolution pathway of carbon dioxide (CO2) evolution pathway. The calculations were performed with density functional theory (DFT) at a DFT + U + J0 and spin polarized level. The CuO was experimentally synthesized and characterized with structural and optical methodologies. The band structure and density of states revealed the rise of band gaps at 1.24 and 1.03 eV with direct and indirect band gap nature, respectively. These values are in accordance with the experimental evidence at 1.28 and 0.96 eV; respectively, which were obtained by UV-Vis DRS. Such a behavior could be related to enhanced photocatalytic activity among copper oxide materials. Experimental evidence such as SEM images and work function measurements were also performed to evaluate the oxide. The redox potential suggests a catalytic character of tenorite (1 1 0) for the CO2 transformation through aldehydes (methanal) intermediate formation. Furthermore, a route through methylene glycol CH2(OH)2 was also explored with the theoretical methodology. The reaction path exhibits an immediate reduction of ▪ into a •OH radical and an [OH]− anion, in the first step. This •OH radical attacks a double bond (C = O) of ▪ to form bicarbonate ([▪]−) and subsequently, carbonic acid (▪). The carbonic acid reacts with other •OH radical to finally form orthocarbonic acid (▪).

Orthoamide und Iminiumsalze, XCIII. Darstellung und Umsetzungen eines vinylogen Orthoamid-Derivats der Kohlensäure mit CH2-aciden Verbindungena

Abstract The preparation of the vinylogue guanidinium salt 10c is described. The reaction of the vinylogue orthocarbonic acid amide derivative 12 with CH2-acidic compounds 14a–s affords the ketene aminals 15a–s. At room temperature the succinimide 19a is deprotonated by 12 to give the vinylogue salt 10e. The bis-ketene aminal 20 is formed in the reaction of 19a with 12 at elevated temperatures. Succinic acid esters 21 do not react cleanly with the orthoamide 12, but mixtures of ketene aminals 23 and bis-ketene aminals 22 are formed. From succinodinitrile (24) and 12 the bis-ketene aminal 25 could be obtained, which is also accessible by the action of the salt 10c with 24 in the presence of sodium hydride.

Novel Stable Compounds in the C-H-O Ternary System at High Pressure.

The chemistry of the elements is heavily altered by high pressure, with stabilization of many new and often unexpected compounds, the emergence of which can profoundly change models of planetary interiors, where high pressure reigns. The C-H-O system is one of the most important planet-forming systems, but its high-pressure chemistry is not well known. Here, using state-of-the-art variable-composition evolutionary searches combined with quantum-mechanical calculations, we explore the C-H-O system at pressures up to 400 GPa. Besides uncovering new stable polymorphs of high-pressure elements and known molecules, we predicted the formation of new compounds. A 2CH4:3H2 inclusion compound forms at low pressure and remains stable up to 215 GPa. Carbonic acid (H2CO3), highly unstable at ambient conditions, was predicted to form exothermically at mild pressure (about 1 GPa). As pressure rises, it polymerizes and, above 314 GPa, reacts with water to form orthocarbonic acid (H4CO4). This unexpected high-pressure chemistry is rationalized by analyzing charge density and electron localization function distributions, and implications for general chemistry and planetary science are also discussed.

Norbornane-exo-cis-2,3-diyl 1′,2′-phenylene orthocarbonate

The title compound (systematic name: 4,7-methano-2,2′-spirobi­[1,3-benzodioxole]), C14H14O4, is an asymmetric spiro ester of orthocarbonic acid and two diols, viz. the aromatic benzene-1,2-diol and the aliphatic vicinal norbornane-exo-cis-2,3-diol. The orthocarbonate mol­ecule is close to having non-crystallographic C s symmetry. The five-membered ring stemming from the aliphatic diol has an envelope conformation. C—O bonds including the spiro-C atom span an approximately 0.07 Å range, but are within 0.02 Å of the respective distances in a density functional theory calculation, i.e. the distance difference is not caused by packing forces. Accordingly, the crystal packing is characterized by weak C—H⋯O and C—H⋯π inter­actions.

Dichlorodiphenoxymethane

The title compound, C13H10Cl2O2, is a mixed derivative of orthocarbonic acid. The non-crystallographic symmetry of the mol­ecule is close to C 2v. The aromatic residues are oriented in a syn conformation with respect to the Cl atoms. The least-squares planes through the phenyl rings enclose an angle of 36.11 (10)°. The C—O bonds at the central carbon are relatively short, and the O—C—O and Cl—C—Cl angles are smaller than the tetra­hedral angle. These metrical peculiarities including a mol­ecular symmetry close to C 2v are also observed in density functional theory (DFT) calculations, thus ruling out the decisive influence of inter­molecular forces in the crystal structure. Accordingly, only few and weak inter­molecular inter­actions are found. At distances smaller than the sum of the van der Waals radii, only two attractive inter­actions are detected: a weak C—H⋯O and a weak C—H⋯Cl hydrogen bond to one of the two potential acceptor atoms each.

1-(Ylomethyl)cyclopentyl 1′,2′-phenylene orthocarbonate

The dispiro title compound (systematic name: 1,4,6,13-tetraoxa-2,3-benzodispiro[4.1.4.2]tridecane), C13H14O4, is an asymmetric orthocarbonic acid ester of an aromatic and an aliphatic vicinal diol. C—O bond lengths at the orthoester centre show a typical difference of about 0.06 Å, as has been observed for related spiro esters with an aliphatic component that does not impose steric strain in the vicinity of the orthocarbonic acid centre. The C—O bond-length differences are also observed in density functional theory (DFT) calculations, thus ruling out a decisive influence of intermolecular forces in the crystal structure. The crystal structure is a polar arrangement of the ester molecules established by van der Waals interactions and, atypically for this class of compounds, by a relatively short C—H...O hydrogen bond.

2,3-Dimethylbutane-2,3-diyl 1,2-phenylene orthocarbonate

The title compound, C13H16O4, is a mixed orthocarbonic acid ester derived from the alcohol components benzene-1,2-diol and 2,3-dimethyl­butane-2,3-diol (pinacol). The spiro­cyclic mol­ecules exhibit noncrystallographic C2 symmetry. The C—O bonds between the spiro centre and the aliphatic di­oxy fragment are markedly shorter than the bonds to the aromatic residue. Neither steric strain, which equalizes the bond lengths in a glucoside analogue, nor the packing of the mol­ecules in the crystal structure are responsible for the large C—O bond-length range, which obviously is a mol­ecular property.

4,6-O-Benzylidene-1-O-methyl-2,3-deoxy-α-D-glucopyranose-2,3-diyl 1,2-phenylene orthocarbonate

The title compound, C21H20O8, is the mixed orthocarbonic acid ester of the alcohol components benzene-1,2-diol and 4,6-O-benzyl­idene-1-O-methyl-α-d-glucopyran­oside. The compound represents the first example of a structurally characterized carbohydrate ester of orthocarbonic acid. Both oxacyclic six-membered rings in the structure adopt a chair conformation. The puckered five-membered ring at the spiro centre is present in a twist conformation. No special inter­actions are observed in the mol­ecular packing.

5,7,13,14-Tetraoxatrispiro[2.2.2.29.26.23]pentadecane

The title compound, C11H16O4, a diol ester of the nonexistent orthocarbonic acid C(OH)4, was prepared for the purpose of collecting NMR data on orthocarbonates and for comparison with similar silicon compounds. The mol­ecule shows chemical but not crystallographic C2 symmetry. The 1,3-dioxane rings adopt chair conformations. The central C atom is in a distorted tetra­hedral environment of four O atoms.

Stabilization of octacoordinate carbon center in metal-containing derivatives of orthocarbonic acid

The electronic and spatial structures of alkali metal compounds CO3M2, CO3M3 +, and CO4M4 (M = Li, Na, K) were investigated by the ab initio (MP2(full)/6-311+G**) and density functional (B3LYP/6-311+G**) methods. The calculated energies of formation decrease in the order E Li > E Na > E K for all structural types, being determined by steric and orbital interactions. Stable structures with octacoordinate carbon are formed in the case of CO4M4 salts.

Molecular structure of unsubstituted oxadiazolic analog of ortho-POPOP and peculiarities of conformational structure of this class of sterically hindered organic compounds

X-ray molecular structure of unsubstituted oxadiazolic ortho-analog of 1,4-bis-(5-phenyl-oxazolyl-2)-benzene (POPOP), synthesized via the 2,5-diphenyl-1,3,4-oxadiazole ortho-carbonic acid was revealed. Its conformation was found to be the same as for the compound obtained earlier from the 2,5-diphenyl-oxazole ortho-carbonic acid. Quantum-chemical modeling was conducted to understand the peculiarities of conformational structure of the investigated class of sterically hindered compounds.

Beiträge zur Synthese von Orthocarbonsäureamiden

The formamidinium salts 11a, c as well as the nitrile 12 react with sodiumhydride/dimethylamine in the presence of trimethylborate to give the ortho formic acid amide 3a. The orthoamides 6a and 16 can be prepared from the iminium salts 15 and 14, resp. by the same procedure. Treatment of the azavinylogous formamidinium salt 15 with sodiumhydride and piperidine or morpholine in the presence of trime-thylborate affords the orthoamides 6c and 6d, resp. By transamination of the azavinylogous aminalester 5a are accessible the orthoamides 6b—d. The vinylogous orthocarbonic acid derivative 17 can be obtained from the salt 14 and sodium alcoholates. The action of sodiumhydride, dimethylamine and trimethylborate on the iminium salt 18 produces a mixture of the orthocarbonic acid derivatives 7a, 8a, 9a. When the guanidinium salt 20 is treated with the same reagents the ortho-amides 3a and 10a are obtained. The reduction of the salt 20 with sodiumhydride in the presence of several activating reagents (e.g. tetrabutyl orthotitanate, aluminiumisopropylate, trimethylborate) affords the orthoamide 3a. The reduction of the iminium salts 18 and 24 does not proceed clean, giving mixtures of various orthoformic acid derivatives. The form-amidine 25 can be prepared by reduction of the salt 15 with sodiumhydride/trimethylborate with good yields. By the action of the corresponding carbanions on the guanidinium salt 20 can be obtained the carboxylic acid orthoamides 26—33. By the same procedure the orthoamides of alkyne carboxylic acids 36a—h, j—n are accessible.

ChemInform Abstract: A New Approach to Spiroorthocarbonates and New Orthocarbonic Acid Derivatives.

AbstractDichlorodiphenoxymethane (II) is coupled with the diols (Ia) ‐ (Ic) to give the orthocarbonates (IIIa) ‐ (IIIc).

Ein neuer Zugang zu Spiroorthocarbonaten und neuen Orthokohlensäure-Derivaten

A New Approach to Spiroorthocarbonates and New Orthocarbonic Acid Derivatives New and simple processes have been developed, which give in good or excellent yields new diphenoxyalkanediyldioxymethanes, symmetrical and unsymmetrical spiroorthocarbonates, spirocyclic orthothiocarbamic acid esters, and acetals of urea by successive or simultaneous substitution of chloro and phenoxy groups contained in dichlorodiphenoxymethane.

ChemInform Abstract: Condensation Reaction of Diethyl Phosphite with Mixed Orthocarbonic Acid Derivatives.

ChemInformVolume 20, Issue 4 Organoelement Compounds ChemInform Abstract: Condensation Reaction of Diethyl Phosphite with Mixed Orthocarbonic Acid Derivatives. V. V. MOSKVA, V. V. MOSKVA Kazanskii khim.-tekhnol. inst. im. KirovaSearch for more papers by this authorV. YU. MAVRIN, V. YU. MAVRIN Kazanskii khim.-tekhnol. inst. im. KirovaSearch for more papers by this author V. V. MOSKVA, V. V. MOSKVA Kazanskii khim.-tekhnol. inst. im. KirovaSearch for more papers by this authorV. YU. MAVRIN, V. YU. MAVRIN Kazanskii khim.-tekhnol. inst. im. KirovaSearch for more papers by this author First published: January 24, 1989 https://doi.org/10.1002/chin.198904221Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume20, Issue4January 24, 1989 RelatedInformation

Malonenamidoxim, Nickelkomplexe und deren ßeaktionsprodukte mit Sauerstoff und Kohlendioxid: Vergleichende Strukturuntersuchungen / Malonenamide Oxime, Nickel Complexes, and their Reaction Products with Oxygen and Carbon Dioxide: Comparative Structural Studies

Abstract Malonenamide oxime [HONC(NH2)CH2C(NH2)NOH = C3H8N4O2] (1), its bis-chelate complex with Ni(II) [Ni(C3H7N4O2)2] (2) and an ethanol solvate of this complex [Ni(C3H7N4O2)2 · 0.6 C2H5OH] (3) are characterized by X-ray structure analysis, as well as a paramagnetic tris-complex [Ni(C3H7N4O2)2(C3H8N4O2)] (4), which forms a catena structure in the crystal. The molecular structures of two reaction products of 2 with air are described: [Ni(C3H5N4O3)2(H2O)2] · 4 H2O (5) has formed by oxidation of the methylene groups and may be taken as a complex of mesoxalamide oxime; [NiC8H16N8O8] · 6 H2O (6) has a macrocyclic ligand which is a derivative of orthocarbonic acid, formed by addition of carbon dioxide to the oxime groups.

Die präparative Chemie derO- undN-funktionellen Orthokohlensäure-Derivate

The methods for the preparation of O- and N-functional orthocarbonic acid derivatives are reviewed, and a survey of the reactions of these compounds with electrophilic and nucleophilic reagents is given. 1. Synthesis of Orthocarbonic Acid Esters 1.1 Reaction of Substituted Trichloromethanes with Alcohols, Alkoxides, Phenols, or Phenoxides 1.2. Reaction of Substituted Dichloromethanes with Alcohols or Phenols 1.3. Reaction of Trialkoxycarbenium Salts with Alkoxides 1.4. Reaction of Cyanic Acid Esters with Alcohols 1.5. Thermolysis of Cyclic Carbonic Acid Derivatives 1.6. Reaction of Carbon Disulfide with Thallium(I) Alkoxides 1.7. Reaction of Carbon Disulfide with Organotin Compounds 1.8. Reaction of Zinc Xanthates with Alcohols 1.9. Transesterification of Orthocarbonic Acid Esters 2. Synthesis of Orthocarbamic Acid Esters 2.1. Reaction of Trihetero-substituted Carbenium Ions with Alkoxides 2.2. Alcoholysis of Tetramethylurea Diethyl Acetal 2.3. Transesterification of Orthocarbamic Acid Esters 2.4. Spirocyclic Orthocarbamic Acid Esters from Organotin Compounds 3. Synthesis of Bis[dialkylamino]-dialkoxymethanes (Tetraalkylurea Dialkyl Acetals) 3.1. Reaction of Bis[dialkylamino]-ethoxycarbenium Tetrafluoroborates with Alkoxides 3.2. Reaction of Tetraalkylurea Dichlorides (Chloroformamidinium Chlorides) with Alcohols or Alkoxides 3.3. Reaction of 2,2-Dichloro-1,3-benzodioxole with Amines 3.4. Spirocyclic Urea Acetals from Organotin Compounds 4. Synthesis of Alkoxytris[dialkylamino]methanes 5. Synthesis of Tetrakis[dialkylamino]methanes 6. Reactions of O- and N-Functional Orthocarbonic Acid Derivatives 6.1. Reactions with Electrophilic Agents 6.2. Reactions with Nucleophilic Agents 6.3. Miscellaneous Reactions of Orthocarbonic Acid Derivatives