Cluster chemistry: XXXVIII. Reactions between M(C2R)(PR′3 (M = Cu,Ag, Au; R = Ph,C6F5; R′ = Me Ph) and H2Os3(CO)10: X-ray structures of Os3Au(μ-CHCHR)(CO)10(PPh3) (R = Ph and C6F5)

The reactions of Os₃(μ-H)₂(CO)₁₀ with a series of Group IB metal acetylide-tertiary phosphine complexes are described. Whereas the compounds M(C₂C₆F₅)(PPh₃) (M = Cu, Ag, Au) afforded the complexes MOs₃(μ-CHCHC₆F₅)(CO)₁₀(PPh₃) cleanly and in high yield, complex mixtures of products were obtained from reactions of the analogous phenylacetylides. The complexes MOs₃(μ-CHCHPh)(CO)₁₀(PPh₃), MOs₃(μ-CHCHPh)(CO)₉(PPh₃)₂ and MOs₃(μ-H)(CO)₁₀(PPh₃) (of known structure), and MOs₃(μ-CHCHPh)(CO)₉(PPh₃)₂ and HMOs₃(CHCPh)(CO)₈ (of unknown structure) were characterised; Au(C₂Ph)(PMe₃) afforded similar derivatives. The reactions proceed by oxidative-addition and hydrogen migration steps; MP bond cleavage reactions also occur to a small extent. The molecular structures of AuOs₃(μ-CHCHC₆R₅)(CO)₁₀(PPh₃) (R = F or H) were determined by X-ray analyses. For R = F, crystals are triclinic, space group P$\text{1}$ with a 9.081(2), b 13.291(2), c 17.419(2) Å, α 84.49(1), β 76.20(2), γ 75.81(2)° and Z = 2; 4622 observed data [I > 2.5σ(I)] were refined to R = 0.027, R_W = 0.031. For R = H, crystals are triclinic, space group P$\text{1}$, with a 9.403(4), b 13.448(3), c 13.774(4) Å, α 83.34(2), β 88.66(3), γ 70.21(3)°, and Z = 2; 4405 observed data [I > 2.5σ(I)] were refined to R = 0.030, R_W = 0.033. The two molecules differ in the orientation of the Ph rings of the PPh₃ groups, but are otherwise similar to Os₃(μ-H)(μ-CHCHBu^t)(CO)₁₀ with the μ-H ligand replaced by the isolobal μ-Au(PPh₃) group.     

Characterization of inclusion complexes of betamethasone-related steroids with cyclodextrins using high-performance liquid chromatography

HPLC was used to study the inclusion complexes formed between various beta- and gamma-cyclodextrins and a series of corticosteroids related to betamethasone. Apparent association constants were measured in acetonitrile-water for a set of 13 steroids. An increase in the stability of the steroid-cyclodextrin complex is observed at lower concentrations of acetonitrile. The effects of the nature of the halide at the 9-position, the location of a double bond within the C-ring, substitution at the 9- and 11-positions, and modification of the D-ring of the steroid backbone were studied. The 11- and 17-positions were found to be critically involved in the inclusion process. Larger apparent association constants were obtained with gamma-cyclodextrin (gamma-CD) than with beta-cyclodextrin (beta-CD) due to the increased diameter of the gamma-CD cavity. Van't Hoff plots were constructed to examine the thermodynamic properties of the inclusion process. Plots constructed using retention factors were found to be nonlinear when gamma-CD was present in the mobile phase. This is due to an increase in the strength of the inclusion complex as temperature decreases. Plots constructed using apparent association constants were linear, indicating that the mechanism of inclusion does not change over the range of temperatures studied (10 to 80 degrees C). Enthalpy-entropy compensation was observed for 11 of the 13 steroids studied. The usefulness of cyclodextrins to achieve the separation of steroids in HPLC is discussed and a practical application for the analysis of a steroid and three potential impurities is described.     

Cyclopentadienyl-ruthenium and -osmium chemistry: XXVIII. Reactions and isomerisation of 1,2-bis(methoxycarbonyl)ethenyl complexes: X-ray structures of Ru{Z)-C(CO2Me)CH(CO2Me)} -(CO)(PPh3)(η-C5H5) · 0.5EtOH,Ru{(E)-C(CO2Me)CH(CO2Me)}(dppe)(η-C5H5) and Ru{C(CO2Me)C(CO2Me)C(CO2Me)CH(CO2Me)} - (PPh3)(η-C5H5)

A reinvestigation of the reaction between C₂(CO₂Me)₂ and RuH(PPh₃)₂(η-C₅H₅) and some related complexes is reported. Initial cis addition is followed by conversion into the trans isomer. In the case of the bis-(PPh₃) complex, isomerisation is followed by chelation of the ester CO group with concomitant displacement of one PPh₃ligand. The resulting chelate complex reacts with CO or CNBu^t to give the (Z)-RuC(CO₂Me)CH(CO₂Me) complexes; the (E)-isomer of the carbonyl complex is obtained by addition of C₂(CO₂Me)₂to RuH(CO)(PPh₃)(η-C₅H₅). The ^1Hand ¹³C NMR spectra are not a reliable guide to assignment of the stereochemistry of the vinyl group. Other products isolated from the initial reaction are the bis-insertion product $\text{Ru{C(CO}{}_2\text{Me)C(CO}{}_2\text{Me)C(CO}{}_2\text{Me)}$CH(CO₂Me)} -(PPh₃)(η-C₅H₅) and the 1/2 PPh₃/C₂(CO₂Me)₂ adduct. The molecular structures of Ru{(Z)-C(CO₂Me)CH(CO₂Me)}(CO)(PPh₃(η-C₅H₅) · 0.5EtOH, Ru{(E)-C(C₂Me)CH(CO₂Me)}(dppe)(η-C₅H₅) and $\text{Ru{C(CO}{}_2\text{Me)C(CO}{}_2\text{Me)C(CO}{}_2\text{-Me)}$CH(CO₂Me)}(PPh₃)(η-C₅H₅) have been determined. The cis isomer is monoclinic, space group P2₁,with a 9.328(8), b 17.385(10), c 10.356(7) Å, β 101.78(3)° and Z = 2; 2107 data with I ≥ 2.5σ(I) were refined to R = 0.076 R_w = 0.085. The trans isomer is triclinic, space group P$\text{1}$, with a 10.404(7) b 11.221(6), c 13.230(9) Å, α 92.67(5), β 110.56(5), γ 106.21(5)° and Z = 2; 2520 data with I ≥ 2.5σ(I) were refined to R = 0.055 R_w = 0.068. The butadienyl complex is monoclinic, space group P2₁/a, with a 19.655(8), b 8.674(4), c 21.060(5) Å, β 116.22(3)° and Z = 4; 2724 data with I ≥ 2.5σ(I) were refined to R = 0.042, R_w = 0.047.     

Light emission from porous silicon single and multiple cavities

Experimental and theoretical techniques are used to examine the effects of microstructuring on the optical properties of multilayer, single and multiple microcavity structures fabricated from porous silicon. Measurements of the reflectivity and photoluminescence spectra of three multilayer samples are presented. The results are modelled using a transfer matrix technique including a negative absorption term to represent the effect of spontaneous emission which gives luminescence. The emitted light is strongly controlled by the optical modes of the structures and very good agreement is observed between theory and experiment.     

High transverse momentumη production in π− p, π+ p,andpp interactions at 280 GeV/c

The inclusive cross sections for η production by the interactions of 280 GeV/c momentum π^?, π⁺, and proton beams in hydrogen have been measured. The kinematical range covered is ?0.45<x _F <0.45, and 4.0<P _T <7.0 GeV/c for Feynmanx _F and transverse momentum respectively. The η to π⁰ cross section ratios are given for the three reactions. The ratio of π^? p to π⁺ p cross sections for η production in the above kinematic ranges is 1.22±0.08±0.11.     

Cluster chemistry: XXXIII. Reactions of [{Au(PPh3)}3O]+ with [Ru3(μ3-C2But)(CO)9]−: X-ray structure of [Ru3Au2(μ3-CCHBut)(CO)9(PPh3)2], containing a t-butylvinylidene ligand attached to a trigonal-bipyramidal Ru3Au2 core

Deprotonation (K[HBBu₃^s]) of HRu₃(μ₃-C₂Bu^t)(CO)₉, followed by reaction of the anion with [O{Au(PPh₃)}₃][BF₄], afforded the known complex Ru₃Au(μ₃-C₂Bu^t)(CO)₉ (9%), the vinylidene cluster Ru₃Au₂(μ₃-CCHBu^t)(CO)₉(PPh₃)₂ (16%) and the hexanuclear Ru₃Au₃(C₂Bu^t)(CO)₈(PPh₃)₃ (3%). The X-ray structure of the pentanuclear complex shows an asymmetric trigonal-bipyramidal Ru₃Au₂ core (Ru, Au at the apices) with the Ru₃ face bridged by a t-butylvinylidene ligand, being σ-bonded to Ru(1) and Ru(3), and η²-coordinated to Ru(2). Crystals are monoclinic, space group P2₁/n with a 19.121(3), b 13.109(3), c 23.649(4) Å, β 106.76(2)° and Z = 4. The structure was solved using 4405 observed diffractometer data, and refined to R 0.044, R_w 0.047.     

Cluster chemistry: XXIX. Preparation of cluster complexes containing aryldiazo ligands: Crystal structure of [HRu3(μ-N2C6H4)(μ3-PhAsCH2AsPh2)(CO)8]

Hydrogenation of [Ru₃(CO)₁₀(L₂)] (L₂ = dppm or dpam) affords [HRu₃(μ₃-PhECH₂EPh₂)(CO)₉] (E = P or As), which is deprotonated by K[HBBu₃^s] . Reactions of the anions with [PhN₂] [PF₆] give [Ru₃(μ-N₂Ph)(μ₃-PhECH₂EPh₂)(CO)₉], which undergo facile cyclometallation reactions when heated, as revealed by an X-ray structure of the title complex.