Piperylene sulfone: a labile and recyclable DMSO substitute

The properties and uses of piperylene sulfone as a new, recyclable dipolar, aprotic solvent for conducting organic reactions are presented.     

Unconventional H‐bonds: SH···N interaction

Quantum calculations at the MP2/aug‐cc‐pVDZ level are used to analyze the SH···N H‐bond in complexes pairing H₂S and SH radical with NH₃, N(CH₃)₃, NH₂NH₂, and NH₂N(CH₃)₂. Complexes form nearly linear H‐bonds in which the S? H covalent bond elongates and shifts its stretching frequency to the red. Binding energies vary from 14 kJ/mol for acceptor NH₃ to a maximum of 22 kJ/mol for N(CH₃)₃ and N(CH₃)₂NH₂. Analysis of geometric, vibrational, and electronic data indicate that the SH···N interaction involving SH is slightly stronger than that in which the closed‐shell H₂S serves as donor. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Pearls on a string: a Z′ = 7 structure for glycyl‐l‐valine

The title peptide, C₇H₁₄N₂O₃, crystallizes with seven independent mol­ecules in the asymmetric unit. All have essentially the same overall conformation, but some flexibility is exhibited by the glycine residue. It appears that the high Z′ value, observed only three times before for an organic compound, permits formation of shorter hydrogen bonds in one of the two head‐to‐tail chains involving the N‐terminal amino groups and the C‐terminal carboxyl­ate groups than found in a hypothetical model structure of glycyl‐l ‐valine with Z′ = 1, and that it furthermore alleviates strain associated with an eclipsed orientation of the amino group.     

Nitromethane as a substitute for nitric oxide in chemical ionization

Nitromethane chemical ionization mass spectra of some alkenes, alkynes and alcohols show that the spectra are similar in many respects to those obtained under nitric oxide chemical ionization conditions.     

Phencyclone Diels-Alder adducts as a new crystalline host. Role of C---H···π and C---H···O interactions

A series of crystalline host compounds, which have a bicyclo[2.2.1]heptene-7-one system, has been synthesized and their inclusion behavior has been investigated. The cycloadduct of phencyclone and N-naphthylmaleimide forms a 1:1 crystalline inclusion complex with 2-butanone. The crystal structure indicates the presence of weak lattice forces supported by C---H···π and C---H···O interactions.     

复合物HNO···H2O2内N-H···O蓝移氢键的理论研究

A theoretical study on the blue-shifted H-bond N-H…O and red-shifted H-bond O-H…O in the complexHNO…H_2O_2 was conducted by employment of both standard and counterpoise-corrected methods to calculate thegeometric structures and vibrational frequencies at the MP2/6-31G(d),MP2/6-31 G(d,p),MP2/6-311 q G(d,p),B3LYP/6-31G(d),B3LYP/6-31 G(d,p) and B3LYP/6-311 G(d,p) levels.In the H-bond N-H…O,the calcu-lated blue shift of N-H stretching frequency is in the vicinity of 120 cm~(-1) and this is indeed the largest theoreticalestimate of a blue shift in the X-H…Y H-bond ever reported in the literature.From the natural bond orbital analy-sis,the red-shifted H-bond O-H…O can be explained on the basis of the dominant role of the hyperconjugation.For the blue-shifted H-bond N-H…O,the hyperconjugation was inhibited due to the existence of significant elec-tron density redistribution effect,and the large blue shift of the N-H stretching frequency was prominently due tothe rehybridization of sp~n N-H hybrid orbital.     

The O–H···O, O–H···N and C–H···O hydrogen bonds in 1,4-dimethylpiperazine mono-betaine monohydrate

1,4-Dimethylpiperazine mono-betaine (1-carboxymethyl-1,4-dimethylpiperazinium inner salt, MBPZ) crystallizes as monohydrate. The crystals are orthorhombic, space group Pccn. Two MBPZ molecules and two water molecules form a cyclic oligomer, (MBPZ·H₂O)₂. The O–H···O and O–H···N hydrogen bonds are of 2.769(1) and 2.902(1) Å, respectively. The dimers interact with the neighboring molecules through the C–H···O hydrogen bonds of 3.234(1) Å. The piperazine ring assumes a chair conformation with the N(4)–CH₃ and N⁺(1)–CH₂COO⁻ groups in the equatorial position and the N⁺(1)–CH₃ group in the axial one. The FTIR spectrum is compared with that calculated by the B3LYP/6-31G(d,p) level of theory.     

KHCoP2O7·2H2O: a novel acidic pyrophosphate

Potassium cobalt hydrogenpyrophosphate dihydrate, KHCoP₂O₇·2H₂O, crystallizes in the orthorhombic space group Pnma. This salt is isotypic with KHMP₂O₇·2H₂O (M = Mn and Zn). The structure consists of alternating layers, built from HP₂O₇³⁻ acidic pyrophosphate groups and CoO₆ octahedra, joined by potassium ions and bridging hydrogen bonds. The Co, K and water O atoms lie on mirror planes. The pyrophosphate group consists of two symmetry‐related PO₄ groups, with the bridging O atom on a mirror plane.     

7-Chloroquinoline: a versatile intermediate for the synthesis of 7-substituted quinolines

A practical synthesis of 7-mono-substituted quinolines has been achieved. Selective reduction of the inexpensive commercial reagent 4,7-dichloroquinoline affords 7-chloroquinoline, which has been converted into more complex 7-mono-substituted quinolines through a series of Pd-catalyzed cross coupling reactions. These studies include the first examples of Suzuki reactions for the preparation of 7-mono-substituted quinolines as well as the first application of the Sonagashira reaction for the synthesis of 7-substituted quinolines. This strategy has been extended to the preparation of 2,7-di-substituted quinolines.     

Phenothiazine as a redox-active DNA base substitute: comparison with phenothiazine-modified uridine

Phenothiazine can be incorporated as a redox-active probe into DNA in two conceptually different ways: the non-nucleosidic DNA base surrogate exhibits similar properties to 10-methylphenothiazine but with no preferential base-pairing properties, whereas the phenothiazine-modified uridine has different optical and electrochemical properties, but exhibits preferred Watson-Crick base pairing with adenine.     

μ3‐η2:η2:η2‐Coordination of Primary Silane on a Triruthenium Plane

A μ₃‐η²:η²:η²‐silane complex, [(Cp*Ru)₃(μ₃‐η²:η²:η²‐H₃SitBu)(μ‐H)₃] ( 2 a ; Cp*=η⁵‐C₅Me₅), was synthesized from the reaction of [{Cp*Ru(μ‐H)}₃(μ₃‐H)₂] ( 1 ) with tBuSiH₃. Complex 2 a is the first example of a silane ligand adopting a μ₃‐η²:η²:η² coordination mode. This unprecedented coordination mode was established by NMR and IR spectroscopy as well as X‐ray diffraction analysis and supported by a density functional study. Variable‐temperature NMR analysis implied that 2 a equilibrates with a tautomeric μ₃‐silyl complex ( 3 a ). Although 3 a was not isolated, the corresponding μ₃‐silyl complex, [(Cp*Ru)₃(μ₃‐η²:η²‐H₂SiPh)(H)(μ‐H)₃] ( 3 b ), was obtained from the reaction of 1 with PhSiH₃. Treatment of 2 a with PhSiH₃ resulted in a silane exchange reaction, leading to the formation of 3 b accompanied by the elimination of tBuSiH₃. This result indicates that the μ₃‐silane complex can be regarded as an “arrested” intermediate for the oxidative addition/reductive elimination of a primary silane to a trinuclear site.     

A polarizable dipole–dipole interaction model for evaluation of the interaction energies for NH···OC and CH···OC hydrogen‐bonded complexes

In this article, a polarizable dipole–dipole interaction model is established to estimate the equilibrium hydrogen bond distances and the interaction energies for hydrogen‐bonded complexes containing peptide amides and nucleic acid bases. We regard the chemical bonds N? H, C?O, and C? H as bond dipoles. The magnitude of the bond dipole moment varies according to its environment. We apply this polarizable dipole–dipole interaction model to a series of hydrogen‐bonded complexes containing the N? H···O?C and C? H···O?C hydrogen bonds, such as simple amide‐amide dimers, base‐base dimers, peptide‐base dimers, and β‐sheet models. We find that a simple two‐term function, only containing the permanent dipole–dipole interactions and the van der Waals interactions, can produce the equilibrium hydrogen bond distances compared favorably with those produced by the MP2/6‐31G(d) method, whereas the high‐quality counterpoise‐corrected (CP‐corrected) MP2/aug‐cc‐pVTZ interaction energies for the hydrogen‐bonded complexes can be well‐reproduced by a four‐term function which involves the permanent dipole–dipole interactions, the van der Waals interactions, the polarization contributions, and a corrected term. Based on the calculation results obtained from this polarizable dipole–dipole interaction model, the natures of the hydrogen bonding interactions in these hydrogen‐bonded complexes are further discussed. © 2013 Wiley Periodicals, Inc.     

PrB7−: A Praseodymium‐Doped Boron Cluster with a PrII Center Coordinated by a Doubly Aromatic Planar η7‐B73− Ligand

The structure and bonding of a Pr‐doped boron cluster (PrB₇⁻) are investigated using photoelectron spectroscopy and quantum chemistry. The adiabatic electron detachment energy of PrB₇⁻ is found to be low [1.47(8) eV]. A large energy gap is observed between the first and second detachment features, indicating a highly stable neutral PrB₇. Global minimum searches and comparison between experiment and theory show that PrB₇⁻ has a half‐sandwich structure with C_6v symmetry. Chemical bonding analyses show that PrB₇⁻ can be viewed as a Pr^II[η⁷‐B₇³⁻] complex with three unpaired electrons, corresponding to a Pr (4f²6s¹) open‐shell configuration. Upon detachment of the 6s electron, the neutral PrB₇ cluster is a highly stable Pr^III[η⁷‐B₇³⁻] complex with Pr in its favorite +3 oxidation state. The B₇³⁻ ligand is found to be highly stable and doubly aromatic with six delocalized π and six delocalized σ electrons and should exist for a series of lanthanide M^III[η⁷‐B₇³⁻] complexes.     

Enzyme electrodes for the sugar substitute aspartame

A sensor of aspartame (l-aspartyl-l-phenylalanine methyl ester) is prepared by chemical immobilization of l-aspartase on an ammonia-selective electrode. Semi logarithmic response (E vs. log C) was observed in the 1 × 10^?3?1 × 10^?2 M range with a slope of ?30 mV/decade. The sensor is stable for more than eight days. The probe is successfully used for the assay of aspartame in commercially available sweeteners.     

Gel-permeation chromatography: Examination of universal calibration procedures for polydimethylsiloxane in a poor solvent

Various procedures for universal calibration in gel-permeation chromatography with polystyrene gels are examined for polystyrene and polydimethylsiloxane fractions. For o-dichlorobenzene at 138°C, experimental intrinsic viscosity–molecular weight data show that the Mark-Houwink exponents are 0.70 and 0.57 for polystyrene and polydimethylsiloxane, respectively. In principle, this difference permits a distinction between the various polymer size parameters proposed for universal calibration. An interpretation of the experimental polydimethylsiloxane calibration for o-dichlorobenzene at 138°C requires a consideration of errors in average molecular weights and errors arising from the use of average molecular weight instead of peak molecular weight. When calibration procedures utilizing hydrodynamic volume and unperturbed dimensions are examined, the difference between them is comparable with experimental error. If the Flory-Fox viscosity expression is employed, the perturbed end-to-end distance (or radius of gyration) and the hydrodynamic volume give equivalent universal calibrations. The experimental data are sufficiently accurate to show that the perturbed dimension determined with the Ptitsyn-Eizner relation does not give an adequate universal calibration.