Syntheses, crystal structures and coordination compounds of some 2-hetarylcyanoximes

2-hetarylcyanoximes which have the general formula HO–NC(CN)–R, where R is a heterocyclic group such as 2-pyridyl, 2-quinolyl, 2-benzthiazolyl etc., have been found to be good multidentate ligands for coordination chemistry. They form intensely colored complexes with iron(II) and bis-compounds with copper(I), which are used in analytical chemistry. Stability constants for anionic Fe2+ tris-cyanoximates were determined. The detailed syntheses and crystal structures of 2-pyridilcyanoxime (HPCO), 2-quinolylcyanoxime (HQCO) and 2-thiazolylcyanoxime (HTLCO) are reported. Molecules of HPCO in the crystal state adopt a non-planar cis–anti conformation. HQCO crystallizes as a monohydrate and this cyanoxime has a trans–anti non-planar conformation in the solid state. Molecules of HTLCO showed a trans–syn planar conformation in the solid state. Crystal structures of other known cyanoxime ligands are reviewed, as well as syntheses and the coordination modes for 2-hetarylcyanoximes in various complexes with s-, p- and d-metals

INFLUENCE OF LIFTING OF MUSCULAR APONEUROTIC TISSUES OF THE HYPOGASTRIUM AREA ON QUALITY OF LIFE IN ABDOMINOPLASTY PATIENTS

An analysis of complex clinical and ultrasonic investigations of the abdominal wall and the following surgery in 42 women with ventral hernia of big size accompanied by the ptosis of the abdomen was made. The patients were divided into two groups, each consisting of 21 patients. The endoprosthesis replacement of defect of the abdominal wall was made with standard polypropylene implant in the first group. The endoprosthesis replacement was complemented by lifting of muscular aponeurotic tissues of the hypogastrium using the implant of the original construction in the second group. The polypropylene endoprosthesis includes the main flap (15×15 cm) with rounded corners and the additional flap (5×40 cm) as a broad band situated at the lower edge of main flap in across-track direction. The increase of physical component of health was noted in 1,8 times in the second group patients and psychological component raised in 2,5 times

Kaj naj zdaj naredi medved, dobi krila?

Two new isostructural cobalt(II) and nickel(II) polynuclear complexes with 2-(phosphonomethyl)aminosuccinic acid, H4PMAS, namely, Na[Co 12(PMAS)6(H2O)17(OH)] ·x2H2O, 1·x2H2O, and Na[Ni 12(PMAS)6(H2O)17(OH)]·xH 2O, 2·xH2O, have been synthesized for the first time from aqueous solutions and studied by single crystal X-ray diffraction, infrared, and UV-visible diffuse reflectance spectroscopy; TG/DTA analysis; and magnetochemistry. Both 1 and 2 crystallize in the rhombohedral crystal system with the R3Ì... space group with 1/6 of the Co12(PMAS) 6 or Ni12(PMAS)6 moieties in the asymmetric unit. The X-ray refinements reveal the presence of 18 water sites, but unit cell charge balance requires that one water molecule must be an OH- anion, an anion which is disordered over the 18 sites. The PMAS4- ligand forms two five-membered and one six-membered chelation ring. Both 1 and 2 contain 24-membered metallacycles as a result of the bridging nature of the PMAS4- ligands. The resulting three-dimensional structures have one-dimensional channels with a sodium cation at the center of symmetry. The temperature dependence of the magnetic susceptibility reveals the presence of weak antiferromagnetic exchange coupling interactions in both 1 and 2. Two exchange coupling constants, J1 = -15.3(7) cm-1 and J 2 = -1.06(2) cm-1 with S1 = S2 = 3/2 for the Co(1)···Co(1) and Co(1) ···Co(2) exchange pathways, respectively, are required for 1, and J1 = -1.17(6) cm-1 and J2 = -4.00(8) cm-1 with S1 = S2 = 1 for the Ni(1)···Ni(1) and Ni(1)···Ni(2) exchange pathways, respectively, are required for 2, in order to fit the temperature dependence of the observed magnetic susceptibilities

First p-linker featuring mercapto and isocyano anchoring groups within the same molecule: synthesis, heterobimetallic complexation and selfassembly on Au(111)

Mercapto (–SH) and isocyano (–N^C) terminated conducting p-linkers are often employed in the evergrowing quest for organoelectronic materials. While such systems typically involve symmetric dimercapto or diisocyano anchoring of the organic bridge, this article introduces the chemistry of a linear azulenic p-linker equipped with one mercapto and one isocyano terminus. The 2-isocyano-6-mercaptoazulene platform was efficiently accessed from 2-amino-6-bromo-1,3-diethoxycarbonylazulene in four steps. The 2-N^C end of this 2,6-azulenic motif was anchrored to the [Cr(CO)5] fragment prior to formation of its 6-SH terminus. Metalation of the 6-SH end of [(OC)5Cr(h1-2-isocyano-1,3-diethoxycarbonyl-6-mercaptoazulene)] (7) with Ph3PAuCl, under basic conditions, afforded X-ray structurally characterized heterobimetallic Cr0/AuI ensemble [(OC)5Cr(m-h1:h1-2-isocyano-1,3-diethoxycarbonyl-6-azulenylthiolate)AuPPh3] (8). Analysis of the 13C NMR chemical shifts for the [(NC) Cr(CO)5] core in a series of the related complexes [(OC)5Cr(2-isocyano-6-X-1,3-diethoxycarbonylazulene)] (X ¼ –N^C, Br, H, SH, SCH2CH2CO2CH2CH3, SAuPPh3) unveiled remarkably consistent inverse-linear correlations d(13COtrans) vs. d(13CN) and d(13COcis) vs. d(13CN) that appear to hold well beyond the above 2-isocyanoazulenic series to include complexes [(OC)5Cr(CNR)] containing strongly electron-withdrawing substituents R, such as CF3, CFClCF2Cl, C2F3, and C6F5. In addition to functioning as a sensitive 13C NMR handle, the essentially C4v-symmetric [(–NC)Cr(CO)5] moiety proved to be an informative, remote, nN^C/nC^O infrared reporter in probing chemisorption of 7 on the Au(111) surface