Synthesis and thermal decomposition of derivatives of acyloxytetraphenylantimony

Acyloxy derivatives of tetra phenylantinmony of the general formula Ph₄SbOC(O)R (R = Alk or Ar) have been synthesized by the reaction of pemaphenylantimony with carboxylic acids. Thermolysis of the compounds obtained affords phenyl carboxylates and triphenylstibine in quantitative yields. One of these compounds (R = CH=CHPh) has been studied by X-ray structural analysis. In this compound, the Sb atom has a trigonal-bipyramidal coordination. The Sb-O(Ph)_eq distances are in the range 2.103(4)-2.140(5) A; the Sb-C(Ph)_ax bond length is 2.167(5) A. The fragment of the residue of cinnamic acid has a delocalized double bond in the carboxylate group.Yu. T. Struchkov deceased in 1995.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 194–198, January, 1996.     

Os3(CO)9{μ3-η1-η1-η2-η2-C(SiMe3)C(Me)C(H)C(Fc)}, the second example of a cluster with the “face” coordination of the metallacyclopentadiene fragment and its conversion to the Os3(μ-H)(CO)8{μ3-η1-η1-η4-η1-C(SiMe3)C(Me)C(H)C(C5H3FeC5H5)} complex with theortho-metallated ferrocene moiety

Os₃(μ-CO)(CO)₉(μ₃-Me₃SiC₂Me) alkyne complexes react with ferrocenylacetylene in hot benzene to form Os₃(CO)₉{μ₃-η¹-η¹-η²-η²-C(SiMe₃)C(Me)C(H)C(Fe)} and a small amount of the isomeric Os₃(CO)₉(μ-η¹-η¹-η⁴-C(SiMe₃)C(Me)C(Fc)C(H)} complex. The structure of the major isomer was confirmed by X-ray structural analysis of the single crystal. Thermolysis of this complex in refluxing benzene affords the Os₃(μ-H)(CO)₈{μ₃-η¹-η¹-η⁴-η¹-C(SiMe₃)C(Me)C(H)(C₅H₃FeC₅H₅)} complex with theortho-metallated ferrocene moiety. The spectral characteristics of clusters with the μ₃-η¹-η¹-η²-η² and μ-η¹-η¹-η⁴ coordinations of the metallacyclopentadiene fragment have been established, which made it possible to choose between the alternative modes of bonding of diene with the trimetallic core.     

Synthesis and stereochemistry of diastereomeric closo-(π,σ-dicyclopentenyl)rhodacarboranes with the agostic C--H...Rh bond

A series of diastereomeric closo-(^1,2-dicyclopentenyl)rhodacarborane complexes with the agostic C--H...Rh bond were synthesized starting from mono-C-substituted anionic nido-carboranes [nido-7-R-7,8-C₂B₉H₁₁]^–. The resulting diastereomeric mixtures were separated into individual isomers by either crystallization or chromatography. The structures and the stereochemistry of the diastereomeric complexes were studied in detail by ¹H and ¹³C NMR spectroscopy. The relative configurations of two key isomers were established by X-ray diffraction analysis. The mechanism of the stereospecific formation of diastereomeric complexes is discussed.     

Chiral derivatives ofexo-metallofulierenes: Synthesis and X-ray study of solvate of platinumfullerene cluster with cyclooctene, η2-C60Pt[(+)-D1OP] · C8H14

A novel optically active exo-metallofullerene derivative, ²-C₆₀Pt[(+)-DIOP] (1) (DIOP is 2,3-o,o'-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphinobutane)), is formed as a result of the cleavage of the chelate metallocycle in Pt[(+)-DIOP]2 and the substitution of the bidentate (+)-DIOP ligand with C₆₀. Cluster 1 was also obtained by replacement of the phosphine ligands in ²-C₆₀Pt(PPh₃)₂ by (+)-DIOP. Compound 1 was identified by its electronic absorption spectra,³¹P NMR spectra, and the elemental analysis data. A singlecrystal X-ray study of the 1 cyclooctene solvate, ²-C₆₀Pt[(+)-DIOP] C₈H₁₄ was performed. Packing of the fullerene cores in a crystal of 1 · C₈H 14 corresponds to the diamond structure subjected to the significant orthorhombic distortions.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1268–1274, May, 1996.     

Kristall- und Molekülstruktur von Tris(1,1-diethyl-3-benzoylthioharnstoff)silber(I)-hydrogensulfid

Crystal and Molecular Structure of Tris(1,1-diethyl-3-benzoylthiourea)silver(I) Hydrogensulfide . The crystal structure of tris(1,1-diethyl-3-benzoylthiourea)silver(I) hydrogensulfide has been determined by X-ray crystal structure analysis. The substance crystallizes monoclinic, space group P2₁/n with a = 8.181, b = 20.216, c = 25.035 Å, β = 98.21° and 4 formula units per unit cell. The structure was solved by heavy atom technique and refined to a final R value of R = 0.046. Silver(I) does not form a chelate with the ligand 1,1-diethyl-3-benzoylthiourea. Three molecules of the ligand coordinate monodentately via the S atoms while a fourth coordination position is occupied by a hydrogensulfide ion. The coordination polyhedron is a distorted tetrahedron.     

Formation and structure of diruthenium complexes Ru2(CO)6−n (PPh3) n {μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} (n=1, 2)

Ruthenium carbonyl triphenylphosphine complexes Ru₂(CO)_6−n (PPh₃) _n {μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} (n=1, 2) were obtained by the reaction of complex Ru₂(CO)₆{μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} containing the ruthenacyclopentadiene moiety with PPh₃ in refluxing toluene. The complexes were characterized by IR and by¹H,¹³C, and³¹P NMR spectroscopy, and by X-ray analysis. The monophosphine derivative is identical to the complex formed by fragmentation of the Ru₃(CO)₈(PPh₃){μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} cluster and contains the PPh₃ ligand at the ruthenium atom of the ruthenacyclopentadiene moiety. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1836–1843, September, 1998     

Cycloaddition of C60 fullerene to stable 2-RSO2-benzonitrile oxides

The interaction of stable 2-RSO₂-benzonitrile oxides1a−c (R=Ph, Bu^t, or PhMeN) with C₆₀ fullerene proceeds at the double (6,6)-bond of fullerene as the [3+2] cycloaddition to form the corresponding isoxazolines2a−c. The molecular structure of compound2b was established by X-ray structural analysis. The interaction of C₆₀ fullerene with 2-(5-methyl-4-nitrothiophene)carbonitrile sulfide, which was obtained by thermolysis of 5-(5′-methyl-4′-nitro-2′-thienyl)1,3,4-oxathiazol-2-one, affords only unstable products. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 118–126, January, 1997.     

Synthesis and characterization of novel monocarbollide exo-closo-(pi-arene)biruthenacarboranes [(PPh3)mClRu(eta6-C6H5R)Ru'CB10H11-n(OMe)n] (where R = H, m = 2, n = 1; R = mu-PPh2, m = 1, n = 0, 1)

The monocarbon carborane [Cs][nido-7-CB(10)H(13)] reacts with the 16-electron [RuCl(2)(PPh(3))(3)] in a solution of benzene/methanol in the presence of N,N,N',N'-tetramethylnaphthalene-1,8-diamine as the base to give a series of 12-vertex monocarbon arene-biruthenacarborane complexes of two types: [closo-2-[7,11-exo-RuClPPh(3)(mu,eta(6)-C(6)H(5)PPh(2))]-7,11-(mu-H)(2)-2,1-RuCB(10)H(8)R] (5, R = H; 6, R = 6-MeO; 7, R = 3-MeO) and [closo-2-(eta(6)-C(6)H(6))-10,11,12-[exo-RuCl(PPh(3))(2)]-10,11,12-(mu-H)(3)-2,1-RuCB(10)H(7)R(1)] (8a, R(1) = 6-MeO; 8b, R(1) = 3-MeO, inseparable mixture of isomers) along with trace amounts of 10-vertex mononuclear hypercloso/isocloso-type complexes [2,2-(PPh(3))(2)-2-H-3,9-(MeO)(2)-2,1-RuCB(8)H(7)] (9) and [2,5-(Ph(3)P)-2-Cl-2-H-3,9-(MeO)(2)-2,1-RuCB(8)H(6)] (10). Binuclear ruthenacarborane clusters of both series were characterized by a combination of analytical and multinuclear NMR spectroscopic data and by single-crystal X-ray diffraction studies of three selected complexes, 6-8. In solution, isomers 8a,b have been shown to undergo the isomerization process through the scrambling of the exo-[RuCl(PPh(3))(2)] fragment about two adjacent triangular cage boron faces B(7)B(11)B(12) and B(8)B(9)B(12).     

X-ray structural study of the first bicluster π-arene complex [η6-PhCo4(CO)9]2CH2 and binuclear complex [η6-PhCr(CO)3]2CH2

It has been established by X-ray structural study that the bicluster cobalt -arene complex of diphenylmethane [⁶-PhCo₄CO₉]₂CH₂ and binuclear complex [⁶-PhCr(CO)₃]₂CH₂ have ans-trans-s-trans conformation in their crystals.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1111–1117, June, 1995.This work was supported by the Russian Foundation for Basic Research (Projects No. 93-03-4028 and 94-03-08338).