Reaction of exo-nido-ruthenacarborane [Cl(Ph3P)2Ru]-5,6,10-(μ-H)3-10-H-7,8-C2B9H8 with bromine

The reaction of bromine with exo-nido-ruthenacarborane [Cl(Ph₃P)₂Ru]-5,6,10-(-H)₃-10-H-7,8-C₂B₉H₈ (1) led to the replacement of the chlorine atom by the bromine atom in the octahedral environment of the ruthenium atom rather than to the substitution in the carborane cage. The structure of [Br(Ph₃P)₂Ru]-5,6,10-(-H)₃-10-H-7,8-C₂B₉H₈ was established by NMR and IR spectroscopy and X-ray diffraction analysis.     

Synthesis and study of the thermal stability of siliconcontaining esters of phosphorus acids. 4. Thermal rearrangement of trimethylsilylmethyl esters of phosphorus acids

NMR spectroscopy has been used to study the thermal rearrangement of siliconeopentyl esters of phosphorus acids Me₃SiCH₂OP(O)R₂ (I, R=CF₃CH₂O, PhO, t-BuCH₂O, Bu). It has been established that in all cases the products of the rearrangement are the respective silyl esters Me₂EtSiOP(O)R₂ (II). The thermal rearrangement of (Me₃SiCH₂O)₂P(O)OR (III, R'=Ph, t-BuCH₂, Me₃SiCH₂) is similar. It has been shown that electronic and steric attributes of the substituents R and R on the phosphorus atom are practically without effect on the extent of the thermal rearrangement. The presence of acidic additives, and initiators and inhibitors of radical reactions did not significantly influence the course of the rearrangement. It was concluded that this rearrangement apparently takes place as a result of heterolysis of the C-OP bond and simultaneous nucleophilic attack on the silicon atom by the phosphoryl part of the molecule.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1155–1158, May, 1991.     

Reaction of α-cyanoacrylic acid and cyanoacrylates with dialkyl and diaryl phosphites

-Cyanoacrylic acid and -cyanoacrylates add dialkyl and diaryl phosphites and diethyl thiophosphite at the C=C double bond in the absence of catalyst. This is an anti-Markovnikov reaction, which yields the corresponding phosphonates and thiophosphonates.A. N. Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1913–1915, August, 1992.     

Synthesis and investigation of mono- and binuclear cyano-bridged complexes of rhodium,ruthenium, and palladium

Binuclear Rh^III and Ru^II complexes of the [M¹-CN-M²]⁺BF ₄ ^– (M¹ and/or M² are (⁵-Cp)(³-C₃H₅)Rh and (⁶-C₆H₆)(³-C₃H₅)Ru) type, heteronuclear organometallic compound (⁵-Cp)(³-C₃H₅)RhCNPd(³-C₃H₅)Cl, and mononuclear Rh^III and Ru^II complexes [(³-C₃H₅)LM(MeCN)]⁺ _BF4 ^– (M = Rh, L = ⁵-Cp; M = Ru, L = ⁶-C₆H₆) were synthesized. An electrochemical study of these compounds in solutions demonstrates that the bond between the bridged CN ligand and the metal atoms is rather strong, and there is no dissociation into mononuclear fragments in solutions. The kinetics of the reaction of [(⁵-Cp)(³-C₃H₅)Rh(MeCN)]⁺ _BF4 ^– with halide ions was studied by electrochemical methods. The ligand exchange proceeds by a bimolecular dissociative-exchange mechanism.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 968–973, May, 1995.     

Binding of ferrocene by cyclic trimeric perfluoro-<Emphasis Type="Italic">o</Emphasis>-phenylenemercury. Synthesis and structure of the first double-decker sandwich complex of a sandwich

The first double-decker sandwich complex of a sandwich was synthesized and fully characterized. The complex was prepared by the reaction of cyclic trimeric perfluoro-o-phenylene-mercury (o-C₆F₄Hg)₃ (1) with ferrocene in an ethereal solution at 20 °C and has the composition {[(o-C₆F₄Hg)₃]₂(Cp₂Fe)} (2). The ferrocene sandwich in 2 is located between the planes of two mercury-containing macrocycles and is coordinated to each of them through donation of the -electrons of the ⁵-Cp ligands to vacant orbitals of the mercury atoms of the adjacent molecule 1. It was concluded that all carbon atoms of the ⁵-Cp rings in complex 2 are involved in the bonding to the macrocycles. Complexation with 1 leads to considerable shifts of the (C-H) and (C-H) bands of ferrocene in the IR spectrum to high frequencies. The structure of complex 2 was determined by X-ray diffraction.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2754–2756, December, 2004.     

Reactions of the Ru3(CO)10(μ-Ph2PCH2PPh2) cluster with enynes RCH=CHC≡CR (R is phenyl or ferrocenyl). Formation of indenone derivatives of triruthenium clusters

The thermal reaction of Ru₃(CO)₁₀(-Ph₂PCH₂PPh₂) (1) with enyne PhCH=CHCCPh afforded the trinuclear ruthenium clusters Ru₃(CO)₆{₃-P(Ph)CH₂PPh₂}{₃-C(Ph)=CHCC(Ph)(1,2-C₆H₄)C(=0)} (2), Ru₃(-H)(CO)₅{₃-P(Ph)CH₂PPh₂}{₃-C(Ph)=CHCC(Ph)(1,2-C₆H₄)C(—0)} (3), and Ru₃(CO)₆(-CO){₃-P(Ph)CH₂PPh₂}{₃-C(C=CPh₂)CH=C(H)Ph} (4) and also two isomers of Ru₃(CO)₅(-CO)(-Ph₂PCH₂PPh₂){₃-C₄Ph₂(CH=CHPh)₂} (5a and 5b). Clusters 2, 3, and 4 were characterized by IR spectroscopy, ¹H and ³¹P NMR spectroscopy, and X-ray diffraction analysis. The reaction of complex 1 with enyne FcCH=CHCCFc gave rise to the Ru₃(CO)₆{₃-P(Ph)CH₂PPh₂}{₃-C(Fc)=CHCC(Fc)(1,2-C₆H₄)C(=0)} (6) and Ru₃(-H)(CO)₅{₃-P(Ph)CH₂PPh₂}{₃-C(Fc)=CHCC(Fc)(1,2-C₆H₄)C(—0)} (7) clusters. According to the spectral data, the latter compounds are isostructural to complexes 2 and 3, respectively.     

Reactions of dodecacarbonyltriruthenium with α,β-unsaturated ketones. Crystal and molecular structures of two reaction products

The thermal reactions of Ru₃(CO)₁₂ with RCOCH=CHPh (R=Me, p-MeC₆H₄) in hydrocarbon solvents lead to the formation of a series of complexes, several of which have been isolated as individual compounds by chromatography. The dinuclear complex Ru₂(-H)(CO)₆(-MeCOCH=CPh) and the tetranuclear complex Ru₄(-H)(-CO)(CO)₇(p-MeC ₆H₄ COCH=CPh)(-p-MeC₆H₄COCH=CPh)(₄-p-MeC₆H₃COCH=CHPh) are characterized by an X-ray structural study. The structures of other reaction products are discussed on the basis of spectral data. The reactions are accompanied by reduction of the starting enones to the corresponding unsaturated ketones.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1285–1293, July, 1993.     

The 13C NMR spectra of π-arenechromium carbonyl complexes

The ¹³C NMR spectra of π-arenechromium complexes XC₆H₅Cr(CO)₂L (where I, L  CO; II, L  PPh₃; X  aliphatic and aromatic substituents) were investigated. The effect of the nature of the substituent X on the chemical shifts of the carbon atoms of the aromatic ring in these complexes was analyzed.It was established that a correlation exists between δ(¹³C) and σ_R (Taft's constant) in complexes I, not only for C(4) nuclei but also for C(3) metal atoms, the difference being that the slopes of the corresponding curves are opposite.     

Stability of a laminated spherical shell

The stability "in the small" of a spherical shell consisting of alternating stiff and soft layers is investigated. The spectra of the bifurcation values of the load are found for a closed shell subject to hydrostatic pressure and their dependence on the buckling mode is studied. The effect of the relative stiffness of the layers on the buckling of the shell is investigated.Moscow Power Engineering Institute. Translated from Mekhanika Polimerov, No. 3, pp. 459–464, May–June, 1976.     

[2 + 2] Photodimerization of the acenaphthylene ruthenium complex [(C5Me4CH2OMe)Ru(η6-C12H8)]+

The [2 + 2] photodimerization of the complex [(C₅Me₄CH₂OMe)Ru(η⁶-C₁₂H₈)]⁺ under visible-light irradiation leads to a mixture of the head-to-head heptacyclene products [(μ-η⁶: η⁶-C₂₄H₁₆)Ru₂(C₅Me₄CH₂OMe)₂]²⁺ (syn- and anti-) with the predominant formation of the syn-isomer; the structures of both isomers were established by X-ray diffraction analysis.