Ivan A. Godovikov

Design and synthesis of new anionic “polymeric ionic liquids” with high charge delocalization

Three novel ionic monomers having highly delocalized anions and electrochemically stable mobile cations, namely, 1-butyl-1-methylpyrrolidinium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethane-sulfonyl)imide, 1-butyl-1-methylpyrrolidinium 1,1-dicyano-1-[(3-(methacryloyloxy)propylsulfonyl)]methanide and 1-butyl-1-methylpyrrolidinium 1-cyano-1-[(3-(methacryloyloxy)propylsulfonyl)]imide were synthesized and characterized. The structure of these monomers was designed to be a mimic of the most highly conductive bis(trifluoromethylsulfonyl)imide, tricyanomethanide and dicyanamide anions. By radical polymerization procedure a series of new anionic “polymeric ionic liquids” (PILs) were prepared. The solubility of these linear PILs, thermal stability, glass transition temperatures, molar masses and ionic conductivities were estimated. An advantage of the novel PILs was demonstrated by the comparison of their ionic conductivity at 25 °C (2.0 × 10−8 ÷ 1.6 × 10−7 S cm−1) with the unmodified poly(1-ethyl-1-methylpyrrolidinium 3-(methacryloyloxy)propane-1-sulfonate) analog. The increase in ionic conductivity is as high as three orders of magnitude and was found to depend on the size of the attached anion. The new ionic monomers were subsequently copolymerized with poly(ethylene glycol) dimethacrylate and poly(ethylene glycol) methyl ether methacrylate. The investigation of the copolymers properties revealed further improvement of the conductivity in approximately two orders of magnitude and the achievement of σ = 4.8 ÷ 6.8 × 10−6 S cm−1) at 40 °C.

Peculiarities of the Complexation of Copper and Silver Adducts of a 3, 5-Bis (trifluoromethyl) pyrazolate Ligand with Organoiron Compounds

Interaction of the copper, {[3,5-(CF(3))(2)Pz]Cu}(3), and silver, {[3,5-(CF(3))(2)Pz]Ag}(3), macrocycles [3,5-(CF(3))(2)Pz = 3,5-bis(trifluoromethyl)pyrazolate] with cyclooctatetraeneiron tricarbonyl, (cot)Fe(CO)(3), was investigated by IR and NMR spectroscopy for the first time. The formation of 1:1 complexes was observed at low temperatures in hexane. The composition of the complexes (1:1) and their thermodynamic characteristics in hexane and dichloromethane were determined. The π-electron system of (cot)Fe(CO)(3) was proven to be the sole site of coordination in solution and in the solid state. However, according to the single-crystal X-ray data, the complex has a different (2:1) composition featuring the sandwich structure. The complexes of ferrocene with copper and silver macrocycles have a columnar structure (X-ray data).

Regiospecific C–N Photocyclization of 2-Styrylquinolines

Regiospecific C-N photocyclization of 2-styrylquinolines resulting in formation of potentially biologically active quino[1,2-a]quinolizinium derivatives was investigated. The presence of strong electron-donating groups in the phenyl ring reveals to be a crucial factor managing photocyclization effectiveness. Introduction of a crown ether moiety allows changing the photoreaction parameters by means of complexation with Mg(ClO4)2.

Synthesis of new ω-amino- and ω-azidoalkyl carboranes

Novel carboranyl amines [7-NH2(CH2)nS-7,8-C2B9H11]− were synthesized by alkylation of 1-mercapto-ortho-carborane with ω-bromoalkylphthalimides followed by removal of the protecting group with hydrazine. closo-Carboranyl azides 1-N3(CH2)nS-1,2-C2B10H11 were prepared by the reaction of the corresponding carboranyl alcohol/iodide with sodium azide and converted to the water soluble nido-form [7-N3(CH2)nS-7,8-C2B9H11]− with ammonium formate in refluxing methanol.

Complexes of (2-methyl-4-oxopent-2-yl)diphenylphosphine oxide with uranyl and neodymium nitrates: synthesis and structures in the solid state and in solution

The reactions of (2-methyl-4-oxopent-2-yl)diphenylphosphine oxide (L) with uranyl and neodymium nitrates afforded complexes with compositions M: L = 1: 2 and 1: 3. These complexes were characterized by X-ray diffraction, IR spectroscopy, and elemental analysis. In the solid complexes, phosphine oxide L has a variable denticity. Studies by 1H and 31P NMR and IR spectroscopy showed that in chloroform, the mononuclear complexes [UO2(O-L)2-(O,O-NO3)2], [Nd(O-L)2(O,O-NO3)3] and [Nd(O-L)3(O,O-NO3)3] are neutral, and the ligand molecules are coordinated to the metal cation through the phosphoryl oxygen atom.

An unusual conversion of paramagnetic [3-Cl-3,3,8-{Ph2P(CH2)nPPh-µ-(C6H4-ortho)}-1,2-(CH3)2-closo-3,1,2-RuIIIC2B9H8] (n=3 and 4) to form the first 18-electron P-phenylene ortho-cycloboronated closo-ruthenacarboranes with a dioxygen ligand.

Treatment of [3-Cl-3,3,8-[Ph2P(CH2)nPPh-µ-(H8] (1, n = 3; 2, n = 4) with an excess of KOH in a 1:1 benzene/methanol mixture at room temperature in air affords new dioxygen closo-ruthenacarborane complexes [3-(η2-O2)-3,3,8-[Ph2P(CH2)nPPh-µ-(H8] (3, n = 3) and (4, n = 4) in 42.5% and 45.8% yield respectively. The structures of dioxygen complexes 3 and 4 were established by single-crystal X-ray diffraction. The IR and multinuclear NMR data [1H, 13C{1H}, 31P{1H} and 11B{1H}] along with 2D HSQC correlation spectra for the new dioxygen closo-ruthenacarboranes are discussed.

Formation of “three-bridge” cobalt-copper commo-cluster with the (B-H)3...Cu bond in the reaction of [Cs][commo-3,3′-Co(1,2-C2B9H11)2] with copper(i) and copper(ii) compounds

Zwitterionic 4,8,8′-exo-{Ph3PCu}-4,8,8′-(μ-H)3-commo-3,3′-Co(1,2-C2B9H9)-(1′,2′-C2B9H10) and ionic [(PPh3)3Cu][commo-3,3′-Co(1,2-C2B9H11)2 complexes were synthesized in moderate yields by the reaction of anionic commo-complex [Cs][commo-3,3′-Co-(1,2-C2B9H11)2]) in a CH2Cl2 solution with anhydrous CuCl2 or CuCl in the presence of PPh3. The complexes were also synthesized by alternative methods and characterized by NMR and X-ray diffraction methods.

First cupracarborane commo-clusters based on the medium-cage nido-5,6-C2B8H12-carborane and molecular structure of [Ph3PEt][commo-9,9′-Cu(nido-7,8-C2B8H11)2]

A reaction of anhydrous CuCl2 with Na salts of the medium-cage carborane [7-X-nido-5,6-C2B8H10]−(X = H or I) derivatives in THF leads to new cupracarborane commo-clusters, [commo-9,9′-Cu(nido-7,8-C2B8H11)2]− and [commo-9,9′-Cu(11-I-nido-7,8-C2B8H10)2]−, in moderate yields. The clusters were isolated as stable [Ph3PEt]+ salts and characterized by 1H, 31P{1H}, and 11B/11B{1H} NMR spectroscopy and X-ray crystallography (for the unsubstituted derivative). The use in this reaction of the reducing agent Na2SO3 considerably increases the yields of both complexes from 25 and 18% to 74 and 68%, respectively.

Metallacarborane clusters based on the middle-cage carborane [5,6-nido-C2B8H12]. Synthesis and the thermal isonido-to-closo rearrangement of the anionic complex [PPN][commo-1,1′-Rh(7-MeO-isonido-2,4-C2B8H9)-(isonido-2,4-C2B8H10)]

The reaction of the middle-cage carborane 5,6-nido-C2B8H12 with the dimeric rhodium complexes [(η2-C8H14)2RhCl]2 or [(η4-C8H12)RhCl]2 in a MeOH/C6H6 mixture gave the anionic commo-rhodacarborane [PPN][commo-1,1′-Rh(isonido-2,4-C2B8H10)2] (as a mixture of meso and dd/ll isomers) and its 7-B-methoxylated derivative [PPN][commo-1,1′-Rh(7-MeO-isonido-2,4-C2B8H9)(isonido-2,4-C2B8H10)] in moderate yields. The latter was subjected to the thermal isonido-to-closo rearrangement to form the new commo-cluster [PPN][commo-1,1′-Rh(closo-2,3-C2B8H9OMe)(closo-2,3-C2B8H10)]. The newly synthesized compounds were characterized by NMR spectroscopy and X-ray diffraction.

New strategy for the synthesis of ladybird beetle azaphenalene alkaloids using a combination of allylboration and intramolecular metathesis. Total synthesis of (±)- Hippocasine and (±)- epi-Hippodamine

A new strategy for assembly a tricyclic skeleton of ladybirds azaphenalene alkaloids (coccinellides) was developed based on the combination of allylboration reaction and intramolecular metathesis. The first key step is the 1,2-organolithiation of 4-picoline with (4,4-dieth-oxybutyl)lithium with subsequent reductive allylation with triallylborane leading to trans-2-allyl-6-(4,4-diethoxybutyl)-4-methyl-1,2,3,6-tetrahydropyridine. The 4,4-diethoxybutyl substituent was further converted to 4-acetoxy-5-hexenyl in four steps, then, the product obtained was involved in the second key step, the intramolecular allylic amination upon treatment with a [Pd] or an [Ir] catalyst giving diastereomeric bicyclic terminal dienes (∼1: 1), which were separated by chromatography. The stereochemistry of one of the dienes is the same as that in alkaloid Hippocasine. The third key step (the intramolecular metathesis reaction) includes the final assembly of the azaphenalene system. The tricyclic derivative obtained contains two differently substituted C=C bonds, selective hydrogenation of one of which (Pd/C) leads to (±)-Hippocasine, whereas exhaustive hydrogenation gives (±)-epi-Hippodamine.