Facile Synthesis of Alkylidene Phthalides by Rhodium-Catalyzed Domino C−H Acylation/Annulation of Benzamides with Aliphatic Carboxylic Acids

The Rh-catalyzed ortho-C(sp²)−H functionalization of 8-aminoquinoline-derived benzamides with aliphatic acyl fluorides generated in situ from the corresponding acids has been developed. This reaction initiated with 8-aminoquinoline-directed ortho-C(sp²)−H acylation, which was accompanied by subsequent intramolecular nucleophilic acyl substitution of amide group to produce alkylidene phthalides This approach exhibits high stereo-selectivity for Z-isomer products, and tolerates a variety of functional groups as well as aliphatic carboxylic acids with diverse structural scaffolds.     

Crystal structure,physical properties and bond valence analysis of NaLuP2O7

Single crystals of a diphosphate NaLuP₂O₇ have been synthesized by the flux method and characterized by single-crystal X-Ray diffraction. NaLuP₂O₇ crystallizes in the monoclinic system with P2₁/n space group with cell parameters: a = 8.9985(8) Å, b = 5.3473(5) Å, c = 12.756(1) Å, β = 103.174° (1), V = 597.67 (9) Å³, Z = 4. Its structure consists of a three-dimensional framework of P₂O₇ units that are corner-shared by LuO₆ octahedra, forming tunnels running parallel to [010] which are occupied by Na atoms. NaLuP₂O₇ powder was characterized by XRD, SEM, FTIR and Raman spectroscopy. The activation energy of (1.49 eV) obtained by electrical measurements suggests the charge carriers to be the sodium cations. The activation energies obtained from impedance and loss spectra were analyzed in order to explain the mechanism of conduction. The correlation between ionic conductivity of NaLuP₂O₇ and its crystallographic structure was investigated and the most probable transport pathway model was determined.     

High Stability of a Phosphenium Ion Allows Umpolung of P--H Bonds

The high intrinsic stability of 1,3,2-diazaphospholenium cations enhances ionic polarization of covalent P--X bonds in P -halogeno- and P -hydrido-diazaphospholenes. The physical properties of the latter suggest a hydridic nature of the P--H bond, and their reactivities display an "Umpolung" as compared to known reaction patterns of phosphines.     

Preparation of Metallaiminophosphoranes and Their Reactivity

Treatment of [Cp*(CO) 2 M{P(NHPh)(OMe) 2 }]PF 6 (M = Fe and Ru) with NaNH 2 gives metallaiminophosphoranes, Cp*(CO) 2 M{P(NPh)(OMe) 2 }. The x-ray structures and reactivity of the complexes are reported.     

NEW CARBON-PHOSPHORUS BOND CONTAINING COMPOUND IN THE REACTION OF 2-ACETYLTHIOPHENE WITH PHOSPHORUS PENTACHLORIDE

Abstract

The treatment of 2-acetylthiophene with phosphorus pentachloride led, besides other products reported in previous studies, to 2-(2-thienyl)-2-chloroethenephosphonic acid in 16% yield. This compound was transformed, in the course of purification attempts, into 2-(2-thienyl)-2-oxoethanephosphonic acid. Full spectroscopic data for both compounds are provided.     

Quick estimation of the Dpb for predicting the strength of chemical bond in situ

An approximate method has been established to calculate the depth of the potential acting on an electron in a molecule at the saddle point along a chemical bond, denoted by Dpb. It is a new indicator which can be used for predicting the strength of a chemical bond. In this work, as a practical application for demonstrating thismethod, we calculated the Dpb of deoxyribonucleosides and ribonucleosides along all C-H and N-H chemical bonds using the method. The results are in fair agreement with those results of previously reported experimental and theoretical observations.     

DFT Study on Homolytic Dissociation Enthalpies of C-I Bonds

The C-I bond dissociation enthalpies （BDE） of various organic iodides were calculated using high-level theoretical methods including MP2 and CCSD（T） with extrapolated basis set as well as a number of density functional theory methods. After systematic evaluation of the theoretical results against available experimental C-I BDEs, it was found that the MPW LYPIM method gave the lowest root mean square error. We, therefore, used this method to examine the substituent effects on different categories of C（sp3）-I and C（sp2）-I bonds. Fur thermore, the remote substituent effects on the C-I BDEs of substituted iodobenzenes and substituted （iodomethyl）benzenes were also investigated at the same level. The C-I BDEs of typical heteroaromatic iodides including five-membered and six-membered heterocyclic iodides were also examined.     

Nature of Alkali- and Coinage-Metal Bonds versus Hydrogen Bonds

We have quantum chemically studied the structure and nature of alkali- and coinage-metal bonds (M-bonds) versus that of hydrogen bonds between A−M and B⁻ in archetypal [A−M⋅⋅⋅B]⁻ model systems (A, B=F, Cl and M=H, Li, Na, Cu, Ag, Au), using relativistic density functional theory at ZORA-BP86-D3/TZ2P. We find that coinage-metal bonds are stronger than alkali-metal bonds which are stronger than the corresponding hydrogen bonds. Our main purpose is to understand how and why the structure, stability and nature of such bonds are affected if the monovalent central atom H of hydrogen bonds is replaced by an isoelectronic alkali- or coinage-metal atom. To this end, we have analyzed the bonds between A−M and B⁻ using the activation strain model, quantitative Kohn-Sham molecular orbital (MO) theory, energy decomposition analysis (EDA), and Voronoi deformation density (VDD) analysis of the charge distribution.     

The Chemical Bond: When Atom Size Instead of Electronegativity Difference Determines Trend in Bond Strength

We have quantum chemically analyzed element−element bonds of archetypal H_nX−YH_n molecules (X, Y=C, N, O, F, Si, P, S, Cl, Br, I), using density functional theory. One purpose is to obtain a set of consistent homolytic bond dissociation energies (BDE) for establishing accurate trends across the periodic table. The main objective is to elucidate the underlying physical factors behind these chemical bonding trends. On one hand, we confirm that, along a period (e. g., from C−C to C−F), bonds strengthen because the electronegativity difference across the bond increases. But, down a period, our findings constitute a paradigm shift. From C−F to C−I, for example, bonds do become weaker, however, not because of the decreasing electronegativity difference. Instead, we show that the effective atom size (via steric Pauli repulsion) is the causal factor behind bond weakening in this series, and behind the weakening in orbital interactions at the equilibrium distance. We discuss the actual bonding mechanism and the importance of analyzing this mechanism as a function of the bond distance.     

大数据时代下的化学经验2.0：基于键能的大规模反应途径预测

报道了一个基于键能数据预测反应途径的可编程算法．运用该算法,成功预测了F₂+CH₃Cl气相反应的最优产物(CF₄)和对应的反应途径．提供了一个启示性的化学经验2.0 的例子,并可能开启大数据时代下的大规模反应途径预测的大门．