Zur disproportionierung der phenylfluorphosphane (C6H5)2PF und (C6H5)PF2

Ph₂P-PF₂Ph₂ has been identified by means ¹⁹F- and ³¹P- NMR spectroscopy as an intermediate product of the disproportionation of Ph₂PF. The disproportionation is catalyzed by acids. The reaction mechanism is discussed. PhPF₂ disproportionates faster in solution in acetonitrile than neat, forming (PhP)₆, instead of (PhP)₅.     

Rate constants for tsomerization of C6H5C(SC6H5)2 ĆH2 radicals to C6H5Ć(SC6H5)CH2SC6H5 radicals based on EPR data

Conclusions The parameters of the Arrhenius equation for the isomerization of PhC(SPh)₂H₂ radicals to Ph(SPh)CH₂. SPh radicals are in agreement with an intramolecular character of the rearrangement, with a 1,2-migration of the thiyl group. These parameters were calculated on the basis of the data that were obtained by the EPR method in the range 10–70°.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2596–2597, November, 1982.     

Über die Kristallstruktur von (C6H5)3SiSH und (C6H5)3SiSBr und die Darstellung des Iodsulfans (C6H5)3SiSI

The Crystal Structure of (C₆H₅)₃SiSH and (C₆H₅)₃SiSBr and the Preparation of the Iodosulfane (C₆H₅)₃SiSI The preparation of the halogenosulfanes Ph₃SiSBr and Ph₃SiSI from Ph₃SiSH and N-halogenosuccinimide is reported. They are characterized by vibrational spectroscopic measurements. Ph₃SiSBr crystallizes in space group P1 with a = 899.3(8) pm, b = 941.3(7) pm, c = 1 051.4(7) pm, α = 109.88(5)°, β = 99.23(6)°, γ = 96.78(6)° and Z = 2. Ph₃SiSH crystallizes in space group P2₁/c with a = 1 879.4(8), b = 966.3(5), c = 1 845.2(9), β = 107.84(4), Z = 8. The halogenosulfanes decompose in polar solvents by formation of sulphur and triphenylsilanhalide.     

The preparation,characterization and reactivity of the cyclometallosilane,cyclo-1,1-di-h5-cyclopentadienyltitana-2,2,3,3,4,4,5,5,-octaphenylpentasilane, (h5-C5H5)2TiSi(C6H5)2[Si(C6H5)2]2Si(C6H5)2

Titanium has been incorporated into a catenated silicon ring by means of the salt elimination reaction of dichlorodi-h⁵-cyclopentadienyltitanium(IV), (I), with 1,4-dilithiooctaphenyltetrasilane, Li₂Si₄(C₆H₅)₈, to yield the title compound (II). II was characterized as a cyclometallopolysilane by means of elemental analyses, base catalyzed hydrolyses, molecular weight determination, infrared and ¹H NMR spectroscopy. Electronic spectral data and electrochemical data are also discussed and support the formulation of II as a disubstituted (h⁵-C₅H₅)₂Ti^IV derivative. The reactivity of II, with CHCl₃, is described in terms of a radical decomposition pathway.     

Novel products from C6H5 + C6H6/C6H5 reactions

To date only one product, biphenyl, has been reported to be produced from C(6)H(5) + C(6)H(6)/C(6)H(5) reactions. In this study, we have investigated some unique products of C(6)H(5) + C(6)H(6)/C(6)H(5) reactions via both experimental observation and theoretical modeling. In the experimental study, gas-phase reaction products produced from the pyrolysis of selected aromatics and aromatic/acetylene mixtures were detected by an in situ technique, vacuum ultraviolet (VUV) single photon ionization (SPI) time-of-flight mass spectrometry (TOFMS). The mass spectra revealed a remarkable correlation in mass peaks at m/z = 154 {C(12)H(10) (biphenyl)} and m/z = 152 {C(12)H(8) (?)}. It also demonstrated an unexpected correlation among the HACA (hydrogen abstraction and acetylene addition) products at m/z = 78, 102, 128, 152, and 176. The analysis of formation routes of products suggested the contribution of some other isomers in addition to a well-known candidate, acenaphthylene, in the mass peak at m/z = 152 (C(12)H(8)). Considering the difficulties of identifying the contributing isomers from an observed mass number peak, quantum chemical calculations for the above-mentioned reactions were performed. As a result, cyclopenta[a]indene, as-indacene, s-indacene, biphenylene, acenaphthylene, and naphthalene appeared as novel products, produced from the possible channels of C(6)H(5) + C(6)H(6)/C(6)H(5) reactions rather than from their previously reported formation pathways. The most notable point is the production of acenaphthylene and naphthalene from C(6)H(5) + C(6)H(6)/C(6)H(5) reactions via the PAC (phenyl addition-cyclization) mechanism because, until now, both of them have been thought to be formed via the HACA routes. In this way, this study has paved the way for exploring alternative paths for other inefficient HACA routes using the PAC mechanism.     

Coordination chemistry of silver(I) with the nitrogen-bridged ligands (C(6)H(5))(2)PN(H)P(C(6)H(5))(2) and (C(6)H(5))(2)PN(CH(3))P(C(6)H(5))(2): the effect of alkylating the nitrogen bridge on ligand bridging versus chelating behavior

The coordination chemistry of silver(I) with the nitrogen-bridged ligands (C(6)H(5))(2)PN(R)P(C(6)H(5))(2) [R = H (dppa); R = CH(3) (dppma)] has been investigated by (31)P NMR and electrospray mass spectrometry (ESMS). Species observed by (31)P NMR include Ag(2)(mu-dppa)(2+), Ag(2)(mu-dppa)(2)(2+), Ag(2)(mu-dppa)(3)(2+), Ag(2)(mu-dppma)(2+), Ag(2)(mu-dppma)(2)(2+), and Ag(eta(2)-dppma)(2)(+). Species observed by ESMS at low cone voltages were Ag(2)(dppa)(2)(2+), Ag(2)(dppa)(3)(2+), Ag(2)(dppma)(2)(2+), and Ag(dppma)(2)(+). (C(6)H(5))(2)PN(CH(3))P(C(6)H(5))(2) showed a strong tendency to chelate, while (C(6)H(5))(2)PN(H)P(C(6)H(5))(2) preferred to bridge. Differences in the bridging versus chelating behavior of the ligands are assigned to the Thorpe-Ingold effect, where the methyl group on nitrogen sterically interacts with the phenyl groups on phosphorus. The crystal structure of the three-coordinate dinuclear silver(I) complex (Ag(2)[(C(6)H(5))(2)PN(H)P(C(6)H(5))(2)](3))(BF(4))(2) has been determined. Bond distances include Ag-Ag = 2.812(1) A, Ag(1)-P(av) = 2.492(3) A, and Ag(2)-P(av) = 2.509(3) A. The compound crystallizes in the monoclinic space group Cc at 294 K, with a = 18.102(4)(o), Z = 4, V = 7261(3) A(3), R = 0.0503, and R(W) = 0.0670.     

混合簇合物(C5H5FeC5H4C2Ph)Co2(CO)6的结构研究

本文用电化学方法和X射线单晶结构分析, 研究了混合簇合物(C5H5FeC5H4C2Ph)Co2(CO)6的结构, 由循环伏安结果, 分别讨论了簇合物中(C5H5FeC5H4和C2O2中心的成键性质, X射线单晶结构分析表明: 晶体属单斜晶系, 空间群为P21, 晶胞参数a=11.845(6), b=8.155(6), c=24.031(6)A, β=90.88°,晶胞中分子数Z=4, 密度Do=1.637g.cm^-^2, 分析了(C5H5FeC5H4C2Ph)Co2(CO)6的结构特点, 并从成键角度讨论了(RC2R^1)Co(CO)6类簇合物的结构随RC2R^1不同而变化的规律。     

Simultaneous thermoanalytical investigations of (C6H5)4AsCl and (C6H5)4PCl under air and argon atmospheres

The thermoanalytical curves of (C₆H₅)₄AsCl (I) and (C₆H₅)₄PCl (II) were generated simultaneously by using a Netzsch simultaneous thermal analyser 409 under static air and dynamic argon atmospheres. The ranges of thermal stability of I and II were found to be 145–310°C and 137–365°C, respectively, and their melting points to be 261 and 278°C. The DTA profiles of I and II differ and can be used for their distinction.