Polarizability effect in transition metal carbonyl complexes

The literature date on substituent influence on the carbonyl stretching frequencies (ν), CO stretching force constants (k), as well as ¹³C NMR carbonyl chemical shifts (δ) have been analyzed for 19 series of the transition metal carbonyl complexes. It was established for the first time that the ν, k and δ values depend not only on the inductive and resonance effects but also on the polarizability of substituents. The polarizability contribution ranges up to 37%.     

An Elementary Method on a Minimization Problem

一、ＴｈｅＰｒｏｂｌｅｍ .Ｌｅｔｆ(ｘ) =ａｘ2 ｂｘ ｃ ａｘ2 ｐｘ ｑ,ｗｈｅｒｅａ >0 ,ｂ2 - 4ａｃ≤ 0ａｎｄｐ2 - 4ａｑ≤ 0 .ＯｕｒＰｒｏｂｌｅｍｉｓ“Ｗｈｅｔｈｅｒｄｏｅｓｍｉｎｘ∈Ｒｆ(ｘ)ｅｘｉｓ?Ｍｏｒｅｏｖｅｒ ,,ｉｆｍｉｎｘ∈Ｒｆ(ｘ)ｅｘｉｓｔｓ,ｔｈｅｎｍｉｎｘ∈Ｒｆ(ｘ)=?ａｎｄｉｎｔｈｉｓｃａｓｅｘ =?” .Ｎａｔｕｒａｌｌｙ ,ｗｅｋｎｏｗｔｈａｔｍｉｎｘ∈Ｒｆ(ｘ)ｅｘｉｓｔｓｆｒｏｍｔｈｅｋｎｏｗｌｅｄｇｅｏｆｍａｔｈｅｍａｔｉｃａｌａｎａｌｙｓｉｓ.Ａｌｓｏ,ｗｅｃａｎｇｉｖｅｔｈｅ…     

EPR parameters of radical ions and polarizability effect

The literature data on substituent influence on the g factors, hyperfine coupling (hfc) constants (a) of the EPR signals and the spin densities (ρ) have been analyzed for 25 series of the organic radical cations and radical anions as well as of the transition metal complexes. The g, a, and ρ values were first established to depend not only on the inductive and resonance effects but also on the polarizability of substituents which can be characterized by the σ(α) constants. The polarizability effect is caused by the partial charge on the radical center. This effect consists in an electrostatic attraction between the charge and the dipole moments induced by this charge in the substituents. The polarizability contribution ranges up to 92%.     

The Synthesis and Properties of New Metal-free and Metallophthalocyanines Containing Four Diloop Macrocyclic Moieties

The synthesis and characterization of new metal-free (9) and metal-containing (Zn, Ni or Cu 10, 11, 12) derivatives of a symmetrically octasubstituted phthalocyanine derived from 21,22-dicyano-2,3,5,6,8,9,11,12,15,17,18,25,26,28-tetradecahydro[1,4,7,12] benzodioxadithiacyclotetradeceno[6,7-b][1,4,7,10,13]benzopentaoxacyclopentadecene (7), which was synthesized in a multi-step reaction sequence, have been described. The novel compouds have been characterized by a combination of elemental analysis, ¹H and ¹³C NMR, IR, UV–vis and MS spectral data.