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Abstract: The reaction of Ru3(CO)12 with 1,3-diferrocenylprop-2-en-1-one,trans-FcCH=CHCOFc (where Fc is ferrocenyl), in boiling hexane afforded the complex MediaObjects/11172_2006_BF02495167_f1.jpg (2c), which was converted into MediaObjects/11172_2006_BF02495167_f2.jpg (3c) upon further heating. These complexes gave the complex MediaObjects/11172_2006_BF02495167_f3.jpg (4) containing two Cl-bridged oxaruthenacycles upon dissolution in CHCl3 or CH2Cl2. The structures of complexes 3 and 4 were established by X-ray diffraction analysis. According to the data of1H NMR spectroscopy, the Cl-bridged complex exists in solutions as a mixture of isomers along with the monomeric form resulting from the cleavage of the halide bridges. All interconversions of the isomers occur with the participation of the monomeric form.

1.A study has been made of the IR spectra in the 4200-33 cm-1 region and Raman spectra in the liquid state and in solutions of tricarbonyl (butadienyl)iron (I) and tricarbonyl-(hexadeuterobutadienyl) iron (II); also, the IR spectrum of (I) in the gas phase has been investigated. A complete assignment of the bands in the vibrational spectra has been proposed on the basis of local symmetry Cs for the butadienyl ligand and C3v for the Fe(CO)3 fragment.2.A calculation has been performed to determine the frequency and forms of the planar vibrations for the C4H6 and C4D6 in the complexes, on the assumption of weak interaction with skeletal vibrations. All of the vibrations of the butadienyl ligand, with the exception of CH stretching vibrations and CCC deformation vibrations, are noncharacteristic.

Conclusions 1.The reaction of methyl ß-iodovinyl ketone and esters of ß-iodoacrylic acid with Fe2(CO)9 produced their tetracarbonyliron p complexes.1.The iodine atom in the complexes (RCOCH = CHI) [Fe(CO)4] (R = Me, MeO) is capable of being replaced by a CpFe(CO)2 group to form hexylcarbonyldiiron complexes.

1.A method was developed for the synthesis of cis- and trans-s-ROCOCH=CHFe(CO)2C5H5 (R=H, CH3, C2H5) by the reaction of the geometric isomers ofß-iodacrylic acid and its esters with [p-C5H5Fe(CO)2]2, in which case the ethylene fragment retains its geometric configuration in the s complex formed.2.A dependence was found for the composition of the products formed in the reaction of cis-C2H5OCOCH= CHI with [C5H5Fe(CO)2]2 versus the temperature.

Conclusions Iron (η2-trans-α,β-dibenzoylethylene)tetracarbonyl (Ia) adds BF3, giving an adduct, which by the action of amines transforms intoπ-allyl-σ-carbamoyl chelate complexes. In the reaction of (Ia) with amines, substitution products of one CO ligand are formed with the composition (η2-PhCOCH=CHCOPh)Fe(CO)3·NH2R.

Conclusions 1.The preparation of allylic cations s-bonded to the p-C5H5Fe(CO)PPh3 group was reported for the first time and some of the reactions of these cations with nucleophiles were studied.2.In the reaction of cations with amines, imine salt complexes [CH3-C(=N+R'R?)CH=CHFe(CO)(PPh3)C5H5-p]X- are formed which, in the case when R' ? R?, are a mixture of stereoisomers. The isomeric composition does not change upon deprotonation of the salts (R'=H) and reprotonation of the neutral imine complexes.

Conclusions 1.Chelate olefincarbamylate complexes of iron carbonyls, which are able to react with electrophilic and nucleophilic reagents, have been synthesized for the first time by the reaction of irontetracarbonyl p-complexes (ITCC) of iminoethers and their salts with amines.2.A new type of carbene compound of iron carbonyls has been synthesized by the ethylation reaction of olefincarbamylate complexes, and ITCC salts of acrylamidines have been obtained by protonation of these complexes.

1.In the reaction of 3-nitroacylophenones with aniline mixtures of two products may be formed: 2-anilino-3-nitropropiophenones (I) and 3-anilinoacrylophenones (II).2.The relative amounts of the products (1) and (II) depend on the nature of the substituents in the benzene nucleus of the acrylophenone: electron-donating groups raise the yield of (I), and electron-accepting groups raise the yield of (II).3.A scheme for the mechanism of the reaction is proposed.

Summary 1.Conditions for the hydrolysis of aryl ß -cyanovinyl ketones to the corresponding ß -aroylacrylic acids and their amides have been established.2.The method of hydrolysis affords the normally difficult to obtain ortho-substituted ß -aroylacrylic acids, in particular ß-(o-nitrobenzoyl)acrylic acid, which can be converted to D,L-kynurenine.

1.A study was made of the effect of steric and electronic factors on the possibility of forming s,p-binuclear complexes of iron.2.A method was developed for the synthesis of the previously unknown compound, s-styryl-p-cyclopentadienyliron dicarbonyl, and a new s,p-binuclear complex was obtained from it.

1.The reaction of the trans- and cis-isomers ofa,ß-dibenzoylethylene (L) with Fe2(CO)9 leads to the formation of the iron tetra- and tricarbonyl complexes, in which the ligand retains its configuration.2.The photochemical and thermal transitions from the iron tetracarbonyl to the iron tricarbonyl complexes were accomplished.3.The direction of the thermal decomposition of the LFe(CO)4 complexes depends on the geometric configuration of the ligand in the complex; for (cis-L)Fe(CO)4 it proceeds to a considerable degree with a reduction of the ligand.

1.In the reaction ofß-chlorovinylketones with Fe2(CO)9, (RCOCH=CHCl)Fe(CO)4 (I) (principal reaction product) and (RCOCH=CHCl)Fe(CO)3 (II).2.A structure analogous to the structure of complexes (diene-1,3)Fe(CO)3 and including coordination of the Fe atom at C=C and C=O bonds was proposed for the complexes (II) on the basis of the IR and NMR spectra.3.The photochemical conversion of (I) to (II) was accomplished.4.The photochemical interaction ofß chlorovinylketones with Fe(CO)5, leading to virtually simultaneous formation of the complexes (I) and (II), was studied.

1.Methods were developed for the preparation of cis- and trans-3-benzoylacrylonitriles.2.The geometric configurations of these isomers were established on the basis of chemical correlations and measurements of the IR and NMR spectra and of dipole moments.

Summary 1.A method was developed for the synthesis of aryl 2-nitrovinyl ketones (3-nitroacrylophenones) (Ar=C6H5, p-CH3C6H4, and p-BrC6H4.2.A study was made of the reactions of these compounds with nucleophilic reagents (OCH3-, CH3OH, OH-).3.The possible mechanism of these reactions is discussed.

Summary 1.2-Cyanovinyl ketones readily undergo addition with nucleophilic reagents at the double bond.2.The addition of the nucleophilic grouping goes in the ß -position to the carbonyl group. On this basis it is concluded that the double bond in 2-cyanovinyl ketones is more strongly “conjugated with the carbonyl group and less strongly with the cyano group.

The vinyl derivatives of germanium form stable p complexes with iron carbonyls.

Conclusions The direct reaction of the acid fluorides of α,Β-unsaturated acids with Fe2CO)9, gives π-olefiniron tetracarbonyl complexes, whereas the corresponding acid chlorides give ferraallyl complexes with a bridge chlorine atom.

Conclusions A radical chain mechanism was proposed for the reaction of triethylgermane with dialkylmercury compounds.

A method was developed for obtaining the O-silylated acetals of ketenes and the esters of a-germylated carboxylic acids, which is based on the reaction of the esters of a-bromocarboxylic acids with bis(triethylsilyl)- and bis(triethylgermyl)mercury.

The action of triphenylphosphine on RCOCH=CHFe(CO)2C5H5 leads to substitution of one CO group to form RCOH=CHFe(CO)(PPh3)C2H5 compounds.

1.Benzenethiol adds to 2-cyanovinyl ketones in the a-position to the CN group.2.The resulting 3-acyl-2-(phenylthio)propionitriles can be oxidized to sulfones and hydrolyzed to the corresponding acids.

The reaction ofß-chlorovinylketone with anion [Re(CO)5]- gives a mixture of cis- and trans-o-complexes RCOCH=CHRe(CO)5 and cyclic compounds with known coordination of the ketone group.

Iron tetracarbonyl and diiron hexacarbonyl complexes are formed when pyridazine and 3,6-dimethylpyridazine are reacted with iron carbonyls.

The reactions of the compounds RCOCH=CHFe(CO)2C5H5 with nucleophilic reagents go analogously to the corresponding reactions ofß-substituted vinyl ketones.

A new method has been developed for the synthesis of substituted bis(silylmethyl)mercury compounds and benzoylgermanes based on the reaction of bis(triethylgermyl)mercury with the corresponding chloromethylsilanes and benzoyl chloride in the presence of atmospheric oxygen.

A general method was developed for the synthesis of bis(silylmethyl)mercury compounds, which is based on the photoinitiated chain free-radical reaction of bis(triethylsilyl)- and bis(triethylgermyl)mercury with chloromethylsilanes.

On the basis of the NMR spectral data on1H,29Si, and199Hg nuclei, it was shown that Hg-X coordination interaction is possible for the compounds (Me3-nXnSiCH2)2Hg, which is manifested to a greater degree for the chloro derivatives.

Conclusions A new method was developed for the synthesis of trialkyl(triorganylsilylalkylthio)silanes and trialkyl(triorganylsilylalkylthio)germanes with the general formula R3MS(CH2)nSiR3 ' (M=Si or Ge) by the reaction of the corresponding triorganylsilylalkenethiols with bis(trialkylsilyl)mercury or bis(trialkylgermyl)mercury.

The photolysis of an equimolar mixture of bis(triethylgermyl)mercury with the benzoyl, m-toluyl, and p-fluorobenzoyl chlorides proceeds to give Hg metal and the corresponding acyltriethylgermanes. In the case of the pivalyl and phenylacetyl chlorides, together with the formation of Hg and Et3GeCl, are generated the acyl radicals Me3CCO and PhCH2CO, and the products of their subsequent transformations are obtained.

The reaction of anisole with the molybdenum and tungsten hexacarbonyls gave the previously unknown antsole complexes (C6H5OCH3)M(CO)3.

The reaction of Fe2(CO)9 with 3,6-diarylpyridazines leads to complexes of the type: ligand·Fe2(CO)6, in which one CO group can be easily replaced by the Ph3P molecule.