X-ray study of volatile Ni(II), Cu(II), and Pd(II) complexes of β-ketoimine pivalyltrifluoroacetone

Synthesis of volatile complexes based on -ketoimine pivalyltrifluoroacetone, C(CH₃)₃C(NH)CH₂COCF₃, is described. The general formula of the complexes is M(L)₂, where M = Cu, Ni, Pd. Complexes of this kind with Ni and Pd were obtained for the first time. The Cu and Pd complexes were found to be isostructural. A comprehensive crystal-chemical study showed that all structures are molecular and built of trans-complexes. The central atom has a square plane environment. The average M-O and M-N distances are nearly equal in all compounds: 1.84 , 1.92 , and 1.98 for Ni, Cu, and Pd complexes, respectively; the mean values of the O-M-N chelate angles are 93.4°, 91.9°, and 92.7°, respectively.Original Russian Text Copyright © 2004 by I. A. Baidina, G. I. Zharkova, N. V. Pervukhina, S. A. Gromilov, and I. K. IgumenovTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 4, pp. 713–722, July–August, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Synthesis and X-Ray Crystal Structure Study of ]2-Methyl-4-(2-methylbenzoyl)-phenoxy] Acetic Acid Hydrazide

Benzophenone analog 3 has been synthesized and characterized by the X-ray diffraction (XRD) method. The compound crystallizes in a monoclinic space group P2₁/c with cell parameters a = 7.701(8) Å, b = 7.151(5) Å, c= 28.323(3) Å, = 104.639(4)°, Z = 4. The structure exhibits intra- and intermolecular hydrogen bonding of the type N–HO, C–HO, and N–HN. The molecules are interlinked through hydrogen bonds forming an infinite chain. This polymeric-like structure may play an important role in biological activity.     

X-ray spectroscopic characterization of Cu2+-phenanthroline complexes intercalated in α-zirconium phosphate

X-ray photoelectron spectroscopy provides evidence that when [Cu(phen)₂]²⁺(phen = 1,10-phenanthroline) is diffused between the layers of -zirconium phosphate, the complex species does not remain intact after intercalation, but some Cu-N bonds are broken, replaced with Cu-O bonds and the released nitrogen atoms can now interact with the PO₃-OH groups of the host. XPS also provides evidence for coordination of the Cu²⁺ ions when they are diffused by ion exchange in the phenanthroline--zirconium phosphate intercalation compound. Although Cu²⁺ and phen are in a 1 : 1 molar ratio in the interlayer region of the host, so that a 1 : 1 coordination could be expected between the two species, the characteristic peaks of the uncoordinated phenanthroline, even though at a low intensity, are still present. The differences between the two Cu(II)-intercalation compounds are discussed.     

Terpenes in organic synthesis

A seven-step synthesis ofS-(+)-hydroprene (S-1) in 20 % overall yield starting fromS-(+)-3,7-dimethyl-1,6-octadiene (2) of 55+-10 % optical purity is described. The introduction of an optical enhancement step in the synthetic sequence at the stage ofS-(–)-3,7-dimethyl-1-octanol (9) raises the optical purity ofS-1 from 50 % to 80 %.For part 13, see. ref.¹ Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 342–348, February, 1993.     

An improved procedure for the synthesis of N-bromoacetyl-β-glycopyranosylamines, derivatives of mono- and disaccharides

An improved procedure for the synthesis of N-bromoacetyl--glycopyranosylamines from the corresponding -glycosylamines was developed. The procedure is applicable to a wide range of derivatives of monosaccharides (hexoses, 2-acetamido-2-deoxyhexoses, hexuronamides, and 6-deoxyhexoses) and some disaccharides. For the derivatives of pentoses and 2-deoxyhexoses, the use of the corresponding -glycosylammonium carbamates was found to be more convenient. N-Bromoacetyl--glycopyranosylamines derived from D-mannose, L-rhamnose, D-glucuronamide, 2-deoxy-D-arabino-hexose, 2-deoxy-D-lyxo-hexose, and melibiose were obtained for the first time.     

Reactions of dodecacarbonyltriruthenium with α,β-unsaturated ketones. Crystal and molecular structures of two reaction products

The thermal reactions of Ru₃(CO)₁₂ with RCOCH=CHPh (R=Me, p-MeC₆H₄) in hydrocarbon solvents lead to the formation of a series of complexes, several of which have been isolated as individual compounds by chromatography. The dinuclear complex Ru₂(-H)(CO)₆(-MeCOCH=CPh) and the tetranuclear complex Ru₄(-H)(-CO)(CO)₇(p-MeC ₆H₄ COCH=CPh)(-p-MeC₆H₄COCH=CPh)(₄-p-MeC₆H₃COCH=CHPh) are characterized by an X-ray structural study. The structures of other reaction products are discussed on the basis of spectral data. The reactions are accompanied by reduction of the starting enones to the corresponding unsaturated ketones.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1285–1293, July, 1993.     

Darstellung der Iminiumsalze CF3?NXCF2+MF6− (X = CH3, F und M = As,Sb) und CF3?NCl = CF2+ AsF6−

Preparation of the Iminium Salts CF₃? NX?CF₂⁺MF₆^? (X = CH₃, F and M = As, Sb) and CF₃? NCl?CF₂⁺ AsF₆^? The preparation of the iminiumsalts CF₃? NX?CF₂⁺ MF₆^? (X = CH₃, F and M = As, Sb) and CF₃? NCl?CF₂⁺ AsF₆^? is reported. The salts were characterized by NMR and infrared spectroscopy. CF₃? NCH₃?CF₂⁺MF₆^? decompose into MF₅ and (CF₃)₂NCH₃.     

Salicylaldimine‐functionalized poly(m‐phenyleneethynylene) as turn‐on chemosensor for ferric ion

A new turn on fluorescent probe for ferric ion based on poly(m‐phenyleneethynylene salicylaldimine) ( PPE‐IM ) has been developed. The preparation of PPE‐IM involves post‐polymerization functionalization of the corresponding polymeric amine, PPE‐AM , via the condensation with salicylaldehyde. The degree of polymerization of both PPE‐IM and PPE‐IM is 17 with polydispersity index of 1.5. In aqueous solution, the polymeric PPE‐IM is highly stable unlike its small molecule analog which is gradually hydrolyzed. The weak fluorescence of initial PPE ‐ IM (λ_em = 470) is greatly enhanced by 300 folds upon the addition of Fe³⁺. The ¹H NMR reveals that the fluorescence enhancement is caused by Fe³⁺‐induced hydrolysis of the imine group. The sensing system shows a detection limit of 0.14 μM of Fe³⁺. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1155–1161