An unusual bis-heteroscorpionate complex with anomalous ligands: [tris(3,4-dibromo-5-phenylpyrazolyl)hydroborato][hydrotris(3-neopentylpyrazolyl)borato]nickel(II).

Tridentate trispyrazolylborate (Tp) ligands, introduced by Trofimenko in 1966, have been widely utilized in metal coordination chemistry because of the relatively facile synthetic modification of their electronic and steric factors. The title heteroscorpionate, [Ni(CHBBrN)(CHBN)], features one ligand, namely hydrotris(3-neopentylpyrazolyl)borate, that has previously displayed variable steric effects, and a brominated ligand, namely tris(3,4-dibromo-5-phenylpyrazolyl)hydroborate, that, atypical in trispyrazolylborate chemistry, coordinates such that the less bulky pyrazole substituent is oriented facing toward the metal ion. The potential molecular threefold symmetry in scorpionates can allow axial chirality.

New homodinuclear tris(3-alkylpyrazolyl)borate complexes of Co and Ni with a tetraacetylethane dianion as a bridging ligand.

Polynuclear complexes and coordination polymers of 3d metals have attracted significant interest evoked by a number of their unique properties. One of the most common approaches to the directed synthesis of coordination polymers is the linking of pre-prepared discrete coordination units by polydentate ligands. The formation of polynuclear complexes is usually a spontaneous process and precise prediction of the products of such reactions is virtually impossible in most cases.

[MODERN VIEW ON INTENSIVE THERAPY OF GASTRO-INTESTINAL HEMORRHAGE].

Basing on analysis of the treatment results in 47 patients for gastro-intestinal hemorrhage, the experience of application of a tranexamic acid in a content of infusion therapy and hemaxam per os was adduced. The data obtained witness the expediency of hemaxam application in a content of therapy on the stage of a hemorrhage letup and for the recurrence prevention.

The role of the bridging group in exchange coupling in dinuclear homo- and heterometallic Ni(II) and Co(II) complexes with oxalate, oxamidate and dithiooxamidate bridges.

Six homodinuclear and two heteronuclear complexes Tp(Np)Co-C(2)O(4)-CoTp(Np) (1), Tp(Np)Co-C(2)O(4)-NiTp(Cy) (2), Tp(Cy)Ni-C(2)O(4)-NiTp(Cy) (3), Tp(Np)Co-C(2)O(2)(NH)(2)-CoTp(Np) (4), Tp(Cy)Ni-C(2)O(2)(NH)(2)-NiTp(Cy) (5), Tp(Np)Co-C(2)S(2)(NH)(2)-CoTp(Np) (6), Tp(Np)Co-C(2)S(2)(NH)(2)-NiTp(Cy) (7), Tp(Cy)Ni-C(2)S(2)(NH)(2)-NiTp(Cy) (8) (Tp(Np) = tris(3-neopentylpyrazolyl)borate, Tp(Cy) = tris(3-cyclohexylpyrazolyl)borate), were synthesized and characterized by mass spectrometry, electronic spectroscopy and X-ray crystallography. These compounds possess similar molecular structures, with the metal ions linked by bridging oxalate (1-3), oxamidate (4 and 5) or dithiooxamidate (6-8) ions. The heteronuclear nature of compounds 2 and 7 was additionally confirmed by high-resolution mass spectrometry.

[Pathogenesis and clinical features of polypous rhinosinusitis].

The paper presents recommendations of the current European and Russian documents concerning pathogenesis of polypous rhinosinusitis (International Consensus Conference on Nasal Polyposis (2006), European documents EAACI - EP3OS (2007), and Summit of the Russian Society of Rhinologists "Nasal polyposis and inflammation" (2009)). The bilateral polypous process in the nasal cavity is considered to be a "special form of rhinosinusitis" in which bacterial superantigens or fungal infection induce chronic eosinophilic inflammation. Researchers of the ENT Department, Rostov State Medical University, undertook analysis of the results of long-term comprehensive examination of patients with polypous rhinosinusitis that included clinical, bacteriological, histomorphological, and allergological studies as well as evaluation of local and systemic immunity.

[On the problem of medicamentous therapy of chronic polypous rhinosinusitis].

Chronic polypous rhinosinusitis (CPS) is currently regarded as a condition requiring medicamentous therapy rather than surgical treatment at the early stages. The choice of therapeutic modalities depends on pathogenetic mechanisms underlying formation of polyps. The International Consensus Conference on Nasal Polyposis (2006) and European documents EAACI - EP3OS (2007) recommend topical (endonasal) glucocorticoids, systemic antibiotics (long-term treatment with low doses of macrolides), antimycotic preparations, and other pharmaceuticals as the main medicinal products for the management of polypous rhinosinusitis (PR).

Copper-homoscorpionate complexes as active catalysts for atom transfer radical addition to olefins.

Cu(I) complexes containing trispyrazolylborate ligands efficiently catalyze the atom transfer radical addition (ATRA) of polyhalogenated alkanes to various olefins under mild conditions. The catalytic activity is enhanced when bulky and electron donating Tpx ligands are employed. Kinetic data have allowed the proposal of a mechanistic interpretation that includes a Cu(II) pentacoordinated species that regulates the catalytic cycle.

Unusual fragmentation of CH2Cl2 by an Ir(III) centre bonded to a doubly metalated Tp(Ms) Ligand (Tp(Ms) = hydrotris(3-mesitylpyrazol-1-yl)borate).

The Ir(III) compound Tp(Ms'')Ir(N2), that contains a pentadentate, doubly metalated 3-mesityl substituted tris(pyrazolyl)borate ligand, induces the cleavage of C-H and C-Cl bonds of CH2Cl2 to yield a highly electrophilic chlorocarbene Ir=C(H)Cl complex.

Unusual polybrominated polypyrazolylborates and their copper(I) complexes: synthesis, characterization, and catalytic activity.

Five new homoscorpionate ligands were prepared and structurally characterized as their Tl complexes, three of which, Tl[TpBr,Ph,Br] (1) (Tp = hydrotris(pyrazolyl)borate, Tl[TpBr,p-Tomicronl,Br] (2), and Tl[TpBr,p-ClPh,Br] (3), are unique in being the first examples of an "atypical" B-N bond to the most sterically hindered pyrazole nitrogen. They contain bromine atoms on the central and outer carbons of the pyrazole ring, with all aryl substituents in the 5-position of the ligand, forming a protective pocket around the B-H bond. These complexes display a rather high B-H stretch frequency (above 2 600 cm-1) in the IR region.

Facile amine formation by intermolecular catalytic amidation of carbon-hydrogen bonds.

A simple copper-based catalytic system has been developed for the carbon-hydrogen amidation reaction. The copper-homoscorpionate complex Tp(Br3)Cu(NCMe) catalyzes the transfer of the nitrene unit NTs (Ts = p-toluenesulfonyl) and its subsequent insertion into the sp(3) C-H bonds of alkyl aromatic and cyclic ethers or the sp(2) C-H bonds of benzene using PhI=NTs as the nitrene source, affording the corresponding trisubstitued NR(1)HTs amines in moderate to high yields. The use of the environmentally friendly chloramine-T has also proven effective, with the advantage that sodium chloride is formed as the only byproduct.

A non-fluorous copper catalyst for the styrene cyclopropanation reaction in a fluorous medium.

The complex Tp(Br3)Cu(NCMe) (1), containing no fluorine atoms, can be dissolved in the perfluoropolyether FOMBLIN and employed as a catalyst for the styrene cyclopropanation reaction with ethyl diazoacetate, with activities and diastereo-selectivities identical to those observed under homogeneous conditions with the advantage of being able to use a fluorous separation technique for catalyst recycling.

Tunable-frequency high-field electron paramagnetic resonance.

A tunable-frequency methodology based on backward wave oscillator sources in high-frequency and -field EPR (HFEPR) is described. This methodology is illustrated by an application to three non-Kramers transition metal ion complexes and one Kramers ion complex. The complexes are of: Ni(II) (S=1) as found in dichlorobistriphenylphosphanenickel(II), Mn(III) (S=2) as found in mesotetrasulfonatoporphyrinatomanganese(III) chloride, Fe(II) (S=2) as found in ferrous sulfate tetrahydrate, and Co(II) (S=3/2) as found in azido(tris(3-tert-butylpyrazol-1-yl)hydroborate)cobalt(II).

[The treatment of purulent-destructive complications of acute surgical diseases and damages of the peritoneal cavity organs].

There were presented the data concerning the results of application of the puncture miniinvasive methods of treatment under ultrasonographic investigation control in 43 patients, suffering purulent-destructive complications of acute diseases and damages of the peritoneal cavity organs. Methods of the puncture sanation and drainage were applied. There was established high efficacy of the methods as the compound of detoxicational therapy and ultimate treatment of false pancreatic cyst and the abdominal cavity abscess.

Copper-catalyzed addition of ethyl diazoacetate to furans: an alternative to dirhodium(II) tetraacetate.

The complexes Tp(x)Cu (Tp(x) = homoscorpionate ligand) catalyze the high yield addition of the carbene fragment :CHCO(2)Et, from ethyl diazoacetate, to furans under mild conditions to give different cyclopropanes and dienes with ratios that depend on the Tp(x) ligand employed, therefore inducing the control of the selectivity in this transformation.

The tautomerism of 1H-pyrazole-3(5)-(N-tert-butyl)carboxamide in the solid state and in solution.

The X-ray crystal structure of 1H-pyrazole-3-(N-tert-butyl)-carboxamide was determined. In the solid state, the 13C and 15N CP/MAS NMR spectra correspond to this tautomer. In solution, both tautomers are present in a ratio that depends on the temperature (at 293 K, 90% 3-substituted/10% 5-substituted).

The coordination chemistry of the hydrotris(3-diphenylmethylpyrazol-1-yl)borate (Tp(CHPh2)) ligand.

The new ligand, hydrotris[3-(diphenylmethyl)pyrazol-1-yl]borate, Tp(CHPh2), has been synthesized and its coordination chemistry was compared with that of the analogous Tp(iPr). The new ligand was converted to a variety of complexes, such as M[Tp(CHPh2)]X (M = Co, Ni, Zn; X = Cl, NCO, NCS), Pd[Tp(CHPh2)][eta3-methallyl], Co[Tp(CHPh2)](acac), and Co[Tp(CHPh2)](scorpionate ligand). Compounds Tl[Tp(CHPh2)], 1, Co[Tp(CHPh2)]Cl, 2, Co[Tp(CHPh2)](NCS)(DMF), 3, Ni[Tp(CHPh2)](NCS)(DMF)2, 4, Co[Tp(CHPh2)](acac), 5, Co[Tp(CHPh2)][Ph2Bp], 6, Co[Tp(CHPh2)][Bp(Ph)], 7, Co[Tp(CHPh2)][Tp], 8, and (Ni[Tp(CHPh2)])2[C2O4](H2O)2, 9, were structurally characterized.

Cyclohexane and benzene amination by catalytic nitrene insertion into C-H bonds with the copper-homoscorpionate catalyst TpBr3CuNCMe.

The complex TpBr3Cu(NCMe) catalyzes, at room temperature, the insertion of a nitrene group from PhINTs into the carbon-hydrogen bond of cyclohexane and benzene, as well as into the primary C-H bonds of the methyl groups of toluene and mesitylene, in moderate to high yield.

Highly regioselective functionalization of aliphatic carbon-hydrogen bonds with a perbromohomoscorpionate copper(I) catalyst.

The complex Tp(Br3)Cu(NCMe) (1) is an excellent catalyst for the regioselective carbene transfer reaction to tertiary C-H bonds of hydrocarbons, at room temperature, using the readily available ethyl diazoacetate (EDA) as the carbene source.

The effect of a 3-benzyl group on the coordination chemistry of homoscorpionate ligands.

New homoscorpionate ligands containing a 3-benzyl substituent, hydrotris(3-benzyl-5-methylpyrazol-1-yl)borate, Tp(Bn,Me), and hydrotris(3-benzyl-4-phenylpyrazol-1-yl)borate, Tp(Bn,4Ph), have been synthesized, and the dynamic behavior of a number of metal complexes was studied by NMR. Structures of the complexes Tl[Tp(Bn,Me)], 1, Tl[Tp(Bn,4Ph)], 2, Co[Tp(Bn,Me)][Tp(Np)], 3, Mo[Tp(Bn,Me)](CO)(2)NO, 4, Co[Tp(Bn,4Ph)][Tp], 5, and Mo[Tp(Bn,Me)](CO)(2)(eta(3)-methallyl), 6, were determined by X-ray crystallography. In the Tp(Bn,Me) ligand, the benzyl group is freely rotating and provides less steric hindrance to the coordinated metal than a neopentyl group, but steric hindrance is increased in the Tp(Bn,4Ph) ligand, where the rotation of the benzyl substituent is restricted by the 4-phenyl substituent.

Catalytic insertion of diazo compounds into N-H bonds: the copper alternative.

The complexes TpxCu (Tpx = homoscorpionate) catalyse the insertion of diazo compounds into nitrogen-hydrogen bonds of amines and amides, under very mild conditions, with quantitative yields being obtained with equimolar ratios of reactants.

A family of highly active copper(I)-homoscorpionate catalysts for the alkyne cyclopropenation reaction.

Equimolar mixtures of ethyl diazoacetate and alkynes can be converted into cyclopropenes in very high yields, at room temperature, through the intermediacy of readily available Cu(I) catalysts containing trispyrazolylborate ligands.

Coordination chemistry of novel scorpionate ligands based on 3-cyclohexylpyrazole and 3-cyclohexyl-4-bromopyrazole.

The ligands [hydrotris(3-cyclohexylpyrazol-1-yl)borate, [Tp(Cy)](-), tetrakis(3-cyclohexylpyrazol-1-yl)borate, [pz(o)Tp(Cy)](-), and hydrotris(3-cyclohexyl-4-bromopyrazol-1-yl)borate, [Tp(Cy,4Br)](-) were synthesized and characterized as their Tl(I) derivatives. They were converted to a variety of tetrahedral LMX and octahedral LML' complexes, as well as to the dinuclear nickel carbonate complex [Ni(Tp(Cy))](2)(CO(3)), 4, and the compound Ni[Tp(Cy,4Br)][pz(Cy,4Br)](3)(H)(2), 5. The structures of Co[Tp(Cy)]Cl, 1, Co[Tp(Cy,4Br)]Cl, 2, Co[Tp(Cy,4Br)]NCS, 3, [Ni(Tp(Cy))](2)(CO(3)), 4, Ni[Tp(Cy,4Br)][pz(Cy,4Br)](3)(H)(2), 5, and Mo[Tp(Cy)](CO)(2)(eta(3)-methallyl), 6, were determined by X-ray crystallography.

Copper(I)-homoscorpionate catalysts for the preferential, kinetically controlled cis cyclopropanation of alpha-olefins with ethyl diazoacetate.

In situ prepared copper catalysts Tp(X)Cu (Tp(X) = homoscorpionate) catalyze the olefin cyclopropanation reaction using ethyl diazoacetate as the carbene source. Very high values of both activity and diastereoselectivity toward the cis isomer have been obtained for styrene, alpha-methylstyrene, 1-hexene, 1-octene, vinyl acetate, n-butyl vinyl ether, 2,5-dimethyl-2,4-hexadiene, and 3,3-dimethyl-1-butene. The effect of the temperature in the diastereoselectivity was almost negligible within the range -10 to +30 degrees C.