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HSAB Principle (hsab + principle)
Selected AbstractsLocal HSAB principle in the conjugate addition of p -substituted thiophenols to cyclohexenoneINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 1 2005Rocío Meza Abstract In the formation of new bonds through the Michel-type addition of thiolates to a ,,,-conjugate system, it is observed that the reaction takes place faster if the thio donor compound contains an electron-rich group or the enone acceptor is highly electron deficient. In contrast, the hard,soft acid,base (HSAB) principle predicts that this reaction is favored when a soft,soft interaction between the reactants takes place. Taking into account that softness is related to a barely electronegative atom of high polarizability, we consider it of interest to analyze the effect of charge transfer of a p -substituent on the softness of sulfur in thiophenols, as well as its impact in the conjugate addition to 2-cyclohexen-1-one. Experiments-in-competition, net charge of X-groups at the p -position of the aromatic ring, the global and local softness at sulfur, and the electrophilicity, obtained by density functional theory (DFT), led to the observation that the reaction is faster for electron attractor thiophenols. The softness at sulfur increases by delocalization of charge through the aromatic ring. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 [source] On the applicability of the HSAB principle through the use of improved computational schemes for chemical hardness evaluationJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 7 2004Mihai V. Putz Abstract Finite difference schemes, named Compact Finite Difference Schemes with Spectral-like Resolution, have been used for a less crude approximation of the analytical hardness definition as the second-order derivative of the energy with respect to the electron number. The improved computational schemes, at different levels of theory, have been used to calculate global hardness values of some probe bases, traditionally classified as hard and soft on the basis of their chemical behavior, and to investigate the quantitative applicability of the HSAB principle. Exchange acid-base reactions have been used to test the HSAB principle assuming the reaction energies as a measure of the stabilization of product adducts. © 2004 Wiley Periodicals, Inc. J Comput Chem 25: 994,1003, 2004 [source] Synthesis and Crystal Structure of a Two-dimensional Silver(I)-Iron(III) Heteronuclear Coordination Polymer: {[Ag,Fe2(SCN)12(H2O)2] [(inaH)2(H2O)2]}nCHINESE JOURNAL OF CHEMISTRY, Issue 1 2004Xiu-Ling Li Abstract The 2-D heteronuclear coordination polymer {[Ag4Fe2(SCN)12(H2O)2] (inaH)2(H2O)2}n (1) (inaH is the abbreviation of protonated isonicotinic acid) with chemical formula C24Ag4Fe2N14O8S12 has been synthesized and characterized by single crystal X-ray diffraction, elemental analysis and IR spectroscopy. The Ag2S2 rings connect two kinds of octahedral geometries of Fe(III) ions, [Fe(NCS)6]3, and Fe(H2O)2(NCS)4], units with bridging thiocyanate ions leading to 2-D [Ag4Fe2(SCN)12(H2O)22, anion framework. Four kinds of rings including the unprecedented thirty-two membered Ag4Fe4(SCN)8 rings share comers or edges in the 2-D anion layer structure. All thiocyanates coordinate to the metal ions according to the HSAB principle with N atoms binding to the Fe(III) ions and with S atoms binding to Ag(I) ions. Pronoated ina cations stabilize the layer structure as counter ions and hydrogen bonds were formed within the pronoated in a cations dimer and between the dimers and the lattice waters. Crystal data: Mr= 1560.44, triclinic, P1, a=0.76082(1) nm, b=0.9234 nm, c= 1.85611(4) nm, a= 103.0170(10)°, ,=93.7780(10)°, y=97.4080(10)°, V= 1.25385(3) nm3, Z=1, ,(Mo K,)=2.650 mm,1, Dc,=2.067 g · cm,3, F(000)=758, R1=0.0412. wR2=0.1003. [source] | ||||||||||