Detail of "855-38-9"

Reference

The isomerization of 1,5-cyclooctadiene catalyzed by bis(acetylacetonato)nickel(II)-triethyldialuminum trichloride-phosphorus ligand

The isomerization of 1,5-cyclooctadiene catalyzed by bis(acetylacetonato)nickel(II)-triethyldialuminum trichloride-phosphorus ligand. Sakakibara, Yasumasa; Oheda, Kenzo; Sakai, Mutsuji; Uchino, Norito (Dep. Polym. Sci. Eng., Kyoto Inst. Technol., Kyoto 606, Japan). Nippon Kagaku Kaishi, (6), 805-10 (Japanese) 1986. CODEN: NKAKB8. ISSN: 0369-4577.In this article, certain chemicals are used. One of their cas registry numbers is 855-38-9 DOCUMENT TYPE: Journal CA Section: 22 (Physical Organic Chemistry) The isomerization of 1,5-cyclooctadiene (1,5-COD) in the presence of catalytic amt. of Ni(acac)2-Et3Al2Cl3-phosphorus ligand (Ni:Al2 = 1:10 molar ratio) was investigated. With added PPh3/Ni = 0~3, 1,5-COD isomerized rapidly at 10~60° in toluene to give bicyclo[3.3.0]oct-2-ene (BCO, transannular product) in high selectivities (90%~) with 1,4-and 1,3-COD (double-bond isomerization products) in trace amts. With PPh3/Ni = 6~10, the isomerization was slow, but the double-bond isomerization products were obtained in fairly high selectivities. By comparison of 17 kinds of phosphorus ligands, the electronic effect of the ligand was obsd. for the isomerization: the reaction rate and the double-bond isomerization products increased with a decrease in the electron-donating ability of the ligands. With one phosphite, 1,4-COD was produced as a main product(selectivity 70%~). On the other hand, the steric effect was not appreciable. The overall rate of formation of BCO and the activation parameters were detd. A reaction mechanism, in which hydridonickel complexes are considered to be the active species, is proposed. .

Ligand exchange and substitution at platinum(II) complexes: evidence for a dissociative mechanism

Ligand exchange and substitution at platinum(II) complexes: evidence for a dissociative mechanism. Romeo, Raffaello; Monsu Scolaro, Luigi; Plutino, Maria Rosaria; Fabrizi de Biani, Fabrizia; Bottari, Giovanni; Romeo, Andrea ( ISMN-CNR, Chimica Analitica e Chimica Fisica, Dipartimento di Chimica Inorganica, Universita di Messina, Messina 98166, Italy). Inorganica Chimica Acta, 350, 143-151 (English) 2003 Elsevier Science B.In this study， 119141-48-9 and 855-38-9 are also used.V. CODEN: ICHAA3. ISSN: 0020-1693. DOCUMENT TYPE: Journal CA Section: 29 (Organometallic and Organometalloidal Compounds) Section cross-reference(s): 22 Square-planar complexes of the type cis-[PtMe2(Me2SO)(PR3)] (1-6) where PR3 represents a series of isosteric tertiary phosphanes (R = 4-MeOC6H4, 4-MeC6H4, Ph, 4-FC6H4, 4-ClC6H4, 4-CF3C6H4) were prepd.; the correlations of 1J(Pt-P) and ligand substitution rates with the basicity of the phosphine ligand were obtained. The coupling consts. 1JPtP with the isotopically abundant 195Pt (33%, I = 1/2) of 1-6, as those of the pyridine cis-[Pt(Me)2(py)(PR3)] derivs. (7-12), show linear dependencies on the basicity of the coordinated phosphine. The rates of low-temp. DMSO exchange for all complexes were measured by 1H NMR isotopic labeling expts. in CDCl3. Pyridine for DMSO substitution kinetics was measured at higher temps. through conventional spectrophotometric techniques. The rates of both processes show no dependence on ligand concn., for each complex the value of the rate of ligand substitution is in reasonable agreement with the value of the rate of ligand exchange at the same temp., and the kinetics are characterized by largely pos. entropies of activation. There is a compensation effect between DHG and DSG, i.e., a greater DHG corresponds to a larger pos. DSG, indicating that all complexes react via the same mechanism. The basicity of the phosphine does not affect significantly the reaction rates. The general pattern of behavior indicates that the rate detg. step for substitution is the dissocn. of the sulfoxide ligand and the formation of a three-coordinated [Pt(Me)2(PR3)] uncharged intermediate. .