scholarly journals Synthesis, Structure and Electrochemical Properties of Acetamide- and Caprolactam-Containing Silicon Catecholates

Molecules ◽  
2021 ◽  
Vol 26 (12) ◽  
pp. 3548
Author(s):  
Eugenia P. Kramarova ◽  
Alexander D. Volodin ◽  
Vadim V. Negrebetsky ◽  
Anastasia D. Shagina ◽  
Teimur M. Aliev ◽  
...  
Keyword(s):  
Nmr Spectra ◽  
Hydrolytic Stability ◽  
Octahedral Geometry ◽  
Redox Properties ◽  
29Si Nmr ◽  
X Ray Diffraction ◽  
X Ray ◽  
X Ray Crystallography ◽  
Nmr Data ◽  
29Si Nmr Spectra

Hexacoordinated heteroligand silicon catecholates, although being prospective as easily soluble compounds with high hydrolytic stability and diverse redox properties, have been insufficiently studied. The transesterification of 1-(trimethoxysilylmethyl)-2-oxohexahydroaze or N-methyl-N-(trimethoxysilylmethyl)acetamide by two equivalents of catechol derivatives in the presence of dicyclohexylamine afforded a series of target compounds in good yield. The complexes were characterized using elemental analysis, FTIR, 1H, 13C and 29Si NMR spectra, X-ray crystallography and cyclic voltammetry. X-ray diffraction confirmed that the silicon atom possesses the octahedral geometry of the SiCO5 polyhedron that remains unchanged in solution as it follows from 29Si NMR data. The compounds demonstrated up to three oxidation waves; and the reduction profile strongly depended on the nature of the substituents on a catecholate anion.

Cyclo-thiazenokomplexe von Vanadium(V) Die Kristallstruktur von (AsPh4)2[V(N3)3(N3S2)]2 · CH2Cl2 / Cyclo-thiazeno Complexes of Vanadium(V) The Crystal Structure of (AsPh4)2[V(N3)3(N3S2)]2 · CH2Cl2

1984 ◽  
Vol 39 (12) ◽  
pp. 1686-1695 ◽  
Author(s):  
Jürgen Hanich ◽  
Magda Krestel ◽  
Ulrich Müller ◽  
Kurt Dehnicke ◽  
Dieter Rehder
Keyword(s):  
Crystal Structure ◽  
Diffraction Data ◽  
Nmr Spectra ◽  
Formula Unit ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
X Ray ◽  
Lattice Constants ◽  
Nmr Data ◽  
Donor Acceptor

An improved synthesis for [VCl2(N3S2)]∞, was found in the reaction of VOCl3 with (NSCl)3; when the reaction is performed in H2CCl2 and (NSCl)3 is used in excess, the thiazyl-solvate [VCl2(N3S2) · NSCl]2 is obtained. [VCl2(N3S2)] reacts with AsPh4Cl to form (AsPh4)2[VCl3(N 3S2)]2; this reacts with AgN3 in CH2Cl2 suspension to yield (AsPh4)2[V (N3)3(N3S2)]2 · CH2Cl2. The compounds were characterized by their IR and 51V NMR spectra. The latter are compared with new 51V NMR data for [VO2Cl2]⊖ and [VOCl4]⊖ ; a decrease of 51V shielding in the order [VO2Cl2]⊖ > [VOCl4]⊖ > [VX3(N3S2)]22⊖ (X - N3 > Cl) is found, which is interpreted in terms of increasing polarizability of the ligands and of ring contributions to the extreme deshielding observed with the thiazenovanadates.The crystal structure of (AsPh4)2[V(N3)3(N3S2)]2 · CH2Cl2 was determined from X-ray diffraction data (1496 observed reflexions, R = 0.058). It crystallizes in the triclinic space group P 1̄ with one formula unit per unit cell and with the lattice constants a - 1087, b = 1317, c = 1350 pm, α = 58.8, β = 85.9, γ = 68.0°. The structure consists of AsPh4⊕ ions, CH2Cl2 molecules and centrosymmetric [V(N3)3(N3S2)]22⊖ anions. In the latter. N3S2 ligands are bonded to the V atoms in a chelate manner with short V = N bonds (189 and 172 pm) forming planar VN3S2 rings. The dimerization is accomplished by V -N donor-acceptor interactions (224 pm) involving one N atom of each VN3S2 ring. The vanadium coordination number of 6 is com pleted by three azido groups with V -N bond distances of 200 to 204 pm.

Structure of a pentacyclic triterpenyl angelate from Loeseliamexicana. 1H 2D-NMR data and stereochemistry

1989 ◽  
Vol 67 (12) ◽  
pp. 2071-2077 ◽  
Author(s):  
M. Jiménez E. ◽  
K. Velézquez ◽  
A. Lira-Rocha ◽  
A. Ortega ◽  
E. Díaz ◽  
...  
Keyword(s):  
Nmr Spectra ◽  
Parent Compound ◽  
2D Nmr ◽  
X Ray Diffraction ◽  
Pentacyclic Triterpene ◽  
Nmr Structure Determination ◽  
X Ray ◽  
H Nmr ◽  
Nmr Data ◽  
Unambiguous Assignment

The total assignment of 1H NMR spectra of a pentacyclic triterpene from Loeseliamexicana was performed using selected 2D-NMR experiments (COSY, NOE). X-ray diffraction data were obtained from the parent compound as supplemental information to the NMR investigations. The data allowed for the unambiguous assignment of the structure and the stereochemistry of the title compound. Keywords: pentacyclic triterpene NMR, 2D NMR of terpenes, X-ray of triterpenes, triterpenyl angelate NMR, X-ray -2D NMR structure determination.

Oligophosphan-Liganden, XIV [1] Bis(distickstoff)molybdän-KomplexeMo(N2)2[PhP(CH2CH2CH2PPh2)2](PR3) / Oligophosphine Ligands, XIV [1] Bis(dinitrogen)molybdenum Complexes Mo(N2)2[PhP(CH2CH2CH2PPh2)2](PR3)

1986 ◽  
Vol 41 (1) ◽  
pp. 70-75 ◽  
Author(s):  
Lutz Dahlenburg ◽  
Bernd Pietsch
Keyword(s):  
Single Crystal ◽  
Diffraction Study ◽  
Nmr Spectra ◽  
Nitrogen Atmosphere ◽  
Octahedral Geometry ◽  
X Ray Diffraction ◽  
Molybdenum Complexes ◽  
X Ray ◽  
Sodium Amalgam ◽  
Dinitrogen Complexes

The reaction of MoCl3(THF)3 with PhP(CH2CH2CH2PPh2)2 in THF/CH2Cl2 gave MoCl3(PhP(CH2CH2CH2PPh2)2) ·CH2CI2 (1). Sodium amalgam reduction of I in the presence of the monotertiary phosphines PMe3-nPhn (n = 0, 1, 2), in THF under nitrogen atmosphere, yielded the bis(dinitrogen) complexesMo(N2)2[PhP(CH2CH2CH2PPh2)2](PMe3) (2),Mo(N2)2[PhP(CH2CH2CH2PPh2)2](PMe2Ph) (3), andMo(N2)2[PhP(CH2CH2CH2PPh2)2I(PMePh2) (4).The homologous PPh3 and i-Pr3P derivatives as well as the attempted tris(dinitrogen) species Mo(N2)2[PhP(CH2CH2CH2PPh2)2] could not be isolated. Compounds 2-4 were assigned trans coordination of the N2 ligands on the basis of their IR, Raman, and 31P NMR spectra. The trans- octahedral geometry of these complexes was also confirmed by a single-crystal X-ray diffraction study performed on 3.

Structures of the 2:1 adducts of benzyne with 2-methylanisole and benzene

2007 ◽  
Vol 85 (7-8) ◽  
pp. 461-465
Author(s):  
Christopher O Bender ◽  
René T Boeré ◽  
Peter W Dibble ◽  
Ryan T McKay
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Gas Phase ◽  
Nmr Spectra ◽  
X Ray Diffraction ◽  
Dft Methods ◽  
X Ray ◽  
X Ray Crystallography ◽  
H Nmr ◽  
Data Points

The 2:1 adduct of benzyne with 2-methylanisole is shown to have the bisbenzotricyclic structure 6,6a,11,11a-tetrahydro-5-methoxy-6-methyl-5,6,11-metheno-5H-benzo[a]fluorene by a single-crystal X-ray diffraction study (C20H18O: Pca21, a = 15.0497(17), b = 9.87783(11), c = 9.6846(11); Z = 4; 1672 data points, R1 = 0.0325). This structure is compared to an unpublished crystal structure of the parent hydrocarbon 6,6a,11,11a-tetrahydro-5,6,11-metheno-5H-benzo[a]fluorene, C18H14. Both structures have also been computed by DFT methods at the B3LYP/6-311(d,p) level of theory. Bond distances and angles between the solid-state measurements and gas-phase calculations are found to agree well; average deviations are well below 1%. The 1H NMR spectra show surprisingly small 3JHH couplings in the central tricyclic cage, but can be assigned using 2D spectroscopy.Key words: Hydrocarbon cages, strained rings, cyclopropane, X-ray crystallography, NMR.

Tele-Substitution Reactions in the Synthesis of a Promising Class of Antimalarials

2020 ◽  
Author(s):  
Marat Korsik ◽  
Edwin Tse ◽  
David Smith ◽  
William Lewis ◽  
Peter J. Rutledge ◽  
...  
Keyword(s):  
Heterocyclic Ring ◽  
Ring System ◽  
Substitution Reactions ◽  
Laboratory Notebook ◽  
Polar Solvents ◽  
X Ray ◽  
X Ray Crystallography ◽  
The Core ◽  
Nmr Data

<p></p><p>We have discovered and studied a <i>tele</i>substitution reaction in a biologically important heterocyclic ring system. Conditions that favour the <i>tele</i>-substitution pathway were identified: the use of increased equivalents of the nucleophile or decreased equivalents of base, or the use of softer nucleophiles, less polar solvents and larger halogens on the electrophile. Using results from X-ray crystallography and isotope labelling experiments a mechanism for this unusual transformation is proposed. We focused on this triazolopyrazine as it is the core structure of the <i>in vivo </i>active anti-plasmodium compounds of Series 4 of the Open Source Malaria consortium.</p> <p> </p> <p>Archive of the electronic laboratory notebook with the description of all conducted experiments and raw NMR data could be accessed via following link <a href="https://ses.library.usyd.edu.au/handle/2123/21890">https://ses.library.usyd.edu.au/handle/2123/21890</a> . For navigation between entries of laboratory notebook please use file "Strings for compounds in the article.pdf" that works as a reference between article codes and notebook codes, also this file contain SMILES for these compounds. </p><br><p></p>

The Electron Effect of Aromatic Group: Control Conformation of 2-Aromatic Cyclododecanone Derivatives

2020 ◽  
Vol 24 (10) ◽  
pp. 1139-1147
Author(s):  
Yang Mingyan ◽  
Wang Daoquan ◽  
Wang Mingan
Keyword(s):  
1H Nmr ◽  
13C Nmr ◽  
Nmr Spectra ◽  
Coupling Constants ◽  
The Other ◽  
Repulsive Interaction ◽  
X Ray Diffraction ◽  
X Ray ◽  
Electron Effect ◽  
Group Control

2-Phenylcyclododecanone and 2-cyclohexylcyclododecanone derivatives were synthesized and characterized by 1H NMR, 13C NMR, HR-ESI-MS and X-ray diffraction. Their preferred conformations were analyzed by the coupling constants in the 1H NMR spectra and X-ray diffraction, which showed the skeleton ring of these derivatives containing [3333]-2-one conformation, and the phenyl groups were located at the side-exo position of [3333]-2-one conformation due to the strong π-π repulsive interaction between the π- electron of benzene ring and π-electron of carbonyl group. The cyclohexyl groups were located at the corner-syn or the side-exo position of [3333]-2-one conformation depending on the hindrance of the other substituted groups. The π-π electron effect played a crucial role in efficiently controlling the preferred conformation of 2-aromatic cyclododecanone and the other 2-aromatic macrocyclic derivatives with the similar preferred square and rectangular conformations.

17O, 13C, and 29Si NMR spectra of some acyloxy- and diacetoxysilanes and acetoxygermanes

1986 ◽  
Vol 51 (11) ◽  
pp. 2582-2589 ◽  
Author(s):  
Antonín Lyčka ◽  
Jaroslav Holeček ◽  
Karel Handlíř ◽  
Josef Pola ◽  
Václav Chvalovský
Keyword(s):  
Periodic System ◽  
Time Scale ◽  
Nmr Spectra ◽  
Group Element ◽  
29Si Nmr ◽  
Carboxyl Group ◽  
29Si Nmr Spectra ◽  
Oxygen Atoms

The 17O, 13C, and 29Si NMR spectra of (CH3)3SiOC(O)R, CH3(XCH2)Si(OC(O)CH3)2, and R3GeOC(O)CH3 compounds are reported. In the 17O NMR spectra at 350 K the only signal is observed with the two latter series, but two well-resolved signals are displayed with the (CH3)3SiOC(O)R compounds. The equivalence of both oxygen atoms in carboxyl group on the NMR time scale is discussed from the viewpoint of a possible coordination of the oxygen atoms to the IVB group element of the periodic system.

Preparation, properties and structure of some intermediate nido- and arachno-monocarbaboranes

1981 ◽  
Vol 46 (10) ◽  
pp. 2345-2353 ◽  
Author(s):  
Karel Baše ◽  
Bohumil Štíbr ◽  
Jiří Dolanský ◽  
Josef Duben
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Nmr Spectra ◽  
Liquid Ammonia ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Starting Compound

The 6-N(CH3)3-6-CB9H11 carbaborane reacts with sodium in liquid ammonia with the formation of 6-CB9H12- which was used as a starting compound for preparing the 4-CB8H14, 9-L-6-CB9H13 (L = (CH3)2S, CH3CN and P(C6H5)3), 1-(η5-C5H5)-1,2-FeCB9H10-, and 2,3-(η5-C5H5)2-2,31-Co2CB9H10- carboranes. The 4-CB8H14 compound was dehydrogenated at 623 K to give 4-(7)-CB8H12 carborane. Base degradation of 6-N(CH3)3-6-CB9H11 in methanol resulted in the formation of 3,4-μ-N(CH3)3CH-B5H10. The structure of all compounds was proposed on the basis of their 11B and 1H NMR spectra and X-ray diffraction was used in the case of the transition metal complexes.

Axially Chiral Bis(α-amino Acid)s and Their Deamino Analogues. Synthesis and Configurational Assignment

1998 ◽  
Vol 63 (2) ◽  
pp. 211-221 ◽  
Author(s):  
Miloš Tichý ◽  
Luděk Ridvan ◽  
Miloš Buděšínský ◽  
Jiří Závada ◽  
Jaroslav Podlaha ◽  
...  
Keyword(s):  
Amino Acid ◽  
Nmr Spectra ◽  
Building Blocks ◽  
X Ray Diffraction ◽  
Amino Groups ◽  
X Ray ◽  
Configurational Assignment ◽  
Symmetry Properties ◽  
Axially Chiral ◽  
Polymeric Structures

The axially chiral bis(α-amino acid)s cis-2 and trans-2 as possible building blocks for polymeric structures of novel type of helicity were prepared. Their configuration has been determined by NMR spectroscopy and, in the case of the trans-isomer, confirmed by single-crystal X-ray diffraction. Analogous pair of stereoisomeric diacids cis-3 and trans-3, devoid of the amino groups, was also prepared and their configuration assigned. The observed differences in the NMR spectra of cis- and trans-isomers of 2 and 3 are discussed from the viewpoint of their different symmetry properties.

Unusual Rearrangement of Naphthalene in the Synthesis of a Novel B8-B8-Bridged Derivative in the [(1,2-C2B9H11)2-3-Co]- Series. X-Ray Structure and 11B NMR Spectra of [8,8'-μ-(CH2-C9H6)-(1,2-C2B9H10)2-3-Co]- (CH3)4N+

1997 ◽  
Vol 62 (5) ◽  
pp. 746-751 ◽  
Author(s):  
Andreas Franken ◽  
Jaromír Plešek ◽  
Christiane Nachtigal
Keyword(s):  
Nmr Spectroscopy ◽  
Single Crystal ◽  
Nucleophilic Substitution ◽  
Nmr Spectra ◽  
X Ray Diffraction ◽  
X Ray ◽  
Unusual Rearrangement ◽  
Multinuclear Nmr Spectroscopy ◽  
11B Nmr ◽  
Isolated Compound

On treatment of the [(1,2-C2B9H11)2Co]- ion with naphthalene in presence of AlCl3 a remarkably bridged [8,8'-μ-(CH2-C9H6)-(1,2-C2B9H10)2-3-Co]- ion is obtained as a single isolated compound. The triatomic -CH2-C9H6- bridge is derived from the rearranged naphthalene nucleus. The mechanism of this reaction is obscure but it does resemble the "Electrophile-Induced Nucleophilic Substitution" reported earlier. The structure of the compound was established by multinuclear NMR spectroscopy and by single crystal X-ray diffraction.

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