Rapid formation of well-ordered self-assembled monolayers of dodecanethiol on polycrystalline gold by microwave irradiation

This article reports a rapid method of preparing self-assembled monolayers of dodecanethiol (C₁₂SH-SAMs) on polycrystalline gold by microwave irradiation (MWI, 650 W, duty cycle is 10%). The qualities of C₁₂SH-SAMs were characterized by both cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results show that the C₁₂SH-SAMs formed by MWI in 120 s (C₁₂SH-SAMs_MWI,120 s) have low ionic permeability (the differential capacitance C_d values are independent of the scan rate and phase angle at 1 Hz Φ_1 Hz = 89 ± 0.9°), excellent electrochemical blocking ability towards the redox probe (the current i_MWI,120 s obtained from CV is lowest when compared to other SAMs and charge transfer resistance R_ct = (1.15 ± 0.19) × 10⁶ Ω cm²), and high surface coverage (99.996 ± 0.001%).     

Cyclic voltammetry of ion transfer across a room temperature ionic liquid membrane supported by a microporous filter

Cyclic voltammetry is used to study the transfer of a series of cations and anions across a room-temperature ionic liquid (RTIL) membrane composed of tridodecylmethylammonium cation (TDMA⁺) and tetrakis(pentafluorophenyl)borate anion (TPFPB⁻), and supported by a thin (∼112 μm) microporous filter. Essential advantage of the thin membrane system is the substantial reduction of the ohmic potential drop, which is compensated in voltammetric measurements. Reversible partition of TPFPB⁻ allows fixing the potential difference at one membrane interface and polarizing the other membrane interface in a defined way. It is shown that the polarized potential window for the interface between an aqueous electrolyte solution and RTIL attains the value of ca. 0.7 V at the ambient temperature of 25 ± 2 °C. Tetraphenylarsonium tetraphenylborate hypothesis is used for the first time to estimate the standard Gibbs energies of ion transfer from water to RTIL and to establish the scale of the absolute potential differences. A linear Gibbs energy relationship is found for the ion transfer from water to RTIL and o-dichlorobenzene.     

Temperature dependence of the surface tension and 0.1 MPa density for 1-Cn-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate with n = 2, 4, and 6

Experimental air–liquid interfacial tension data and density data are presented for three 1-C_n-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphates (FAP), [C_nMIM][(C₂F₅)₃PF₃], with n = 2, 4, and 6, measured at atmospheric pressure in the temperature range from 267 K to 360 K using the Krűss K100MK2 tensiometer. The accuracy of the surface tension measurements was checked by employing the Wilhelmy plate and the du Noüy ring methods in parallel. The combined standard uncertainty associated with the Wilhelmy plate method is estimated to be ±0.1 mN · m⁻¹. The density data were obtained using buoyancy method with an estimated standard uncertainty less then ±0.4 kg · m⁻³ (3 · 10⁻⁴ϱ). The chloride anions decrease the density of the tris(pentafluoroethyl)trifluorophosphates of interest up to six times more effectively than they decrease the density of the imidazolium based tetrafluoroborates. A QSPR analysis of the surface tension of imidazolium based ionic liquids with BF₄, TFA, DCA, FAP, NTf₂, and PF₆ anions indicates, that the FAP ionic liquids fit well into the analyzed group of imidazolium based ionic liquids while those having hexafluorophosphate anion show anomalously high deviations of the experimental surface tension from the values predicted by the QSPR model.     

Low-temperature heat capacity and standard molar enthalpy of formation of 9-fluorenemethanol (C14H12O)

Low-temperature heat capacities of the 9-fluorenemethanol (C₁₄H₁₂O) have been precisely measured with a small sample automatic adiabatic calorimeter over the temperature range between T=78 K and T=390 K. The solid–liquid phase transition of the compound has been observed to be T_fus=(376.567±0.012) K from the heat-capacity measurements. The molar enthalpy and entropy of the melting of the substance were determined to be Δ_fusH_m=(26.273±0.013) kJ · mol⁻¹ and Δ_fusS_m=(69.770±0.035) J · K⁻¹ · mol⁻¹. The experimental values of molar heat capacities in solid and liquid regions have been fitted to two polynomial equations by the least squares method. The constant-volume energy and standard molar enthalpy of combustion of the compound have been determined, Δ_cU(C₁₄H₁₂O, s)=−(7125.56 ± 4.62) kJ · mol⁻¹ and Δ_cH_m^∘(C₁₄H₁₂O, s)=−(7131.76 ± 4.62) kJ · mol⁻¹, by means of a homemade precision oxygen-bomb combustion calorimeter at T=(298.15±0.001) K. The standard molar enthalpy of formation of the compound has been derived, Δ_fH_m^∘(C₁₄H₁₂O,s)=−(92.36 ± 0.97) kJ · mol⁻¹, from the standard molar enthalpy of combustion of the compound in combination with other auxiliary thermodynamic quantities through a Hess thermochemical cycle.     

Esterification of (RS)-Ibuprofen by native and commercial lipases in a two-phase system containing ionic liquids

Four commercially available lipases and two native lipases from Aspergillus niger AC-54 and Aspergillus terreus AC-430 were used for the resolution of (RS)-Ibuprofen in systems containing the ionic liquids [BMIM][PF₆] and [BMIM][BF₄]. The lipases showed higher conversion in a two-phase system using [BMIM][PF₆] and isooctane compared to that in pure isooctane. Although the best enzyme was a commercially available lipase from Candida rugosa (E = 8.5), another native lipase, produced in our laboratory, from A. niger gave better enantioselectivity (E = 4.6) than the other lipases tested (E = 1.9–3.3.). After thorough optimization of several reaction conditions (type and ratios of isooctane/ionic liquid, amount of enzyme, and reaction time), the E-value of A. niger lipase (15% w/v) could be duplicated (E = 9.2) in a solvent system composed of [BMIM][PF₆] and isooctane (1:1) after 96 h of reaction.     

A ruthenium(II) complex with the propionate ion: Synthesis,characterization and cytotoxic activity

The complex [Ru(η²-O₂CCH₂CH₃)(dppe)₂]PF₆ (dppe = 1,2-bis(diphenylphosphino)ethane) was prepared and characterized by elemental analysis, spectroscopic techniques, X-ray crystallography, HRESIMS and HRESIMS/MS. The characterization data are consistent with a cis arrangement for the dppe ligands and a bidentate coordination of the propionate ligand through carboxylate oxygens. Cytotoxicity assays were carried out on human and murine cancer and normal cell lines. In general, the [Ru(η²-O₂CCH₂CH₃)(dppe)₂]PF₆ complex was more cytotoxic than both its precursor cis–[RuCl₂(dppe)₂] and the reference metallodrug cisplatin. The best results against the HepG2 human tumour cell line and S180 murine tumour cell line were found with IC₅₀ values of 6.5 ± 0.2 and 0.18 ± 0.03 μM, respectively.     

Study on the phase behaviour and thermodynamic properties of ionic liquids containing imidazolium cation with ethanol at several temperatures

Experimental densities, speeds of sound and refractive indices of the binary mixtures of ethanol with MMIM MeSO₄ (1,3-dimethylimidazolium methyl sulfate), BMIM MeSO₄ (1-butyl-3-methylimidazolium methyl sulfate), BMIM PF₆ (1-butyl-3-methylimidazolium hexafluorophosphate), HMIM PF₆ (1-hexyl-3-methylimidazolium hexafluorophosphate) and OMIM PF₆ (1-methyl-3-octylimidazolium hexafluorophosphate) were determined from T = (293.15 to 303.15) K. Excess molar volumes, changes of refractive index on mixing and deviations in isentropic compressibility for the above systems were calculated. The (liquid + liquid) equilibrium (LLE) data of (IL + ethanol) were carried out experimentally and the NRTL and UNIQUAC correlative equation was applied to these mixtures.     

An SFG/DFG investigation of CN− adsorption at an Au electrode in 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl) amide ionic liquid

In this paper we report an SFG/DFG investigation of the adsorption of CN^? – used as a probe molecule to study the electrochemical double-layer structure – at a polycrystalline Au electrode in 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl) amide ([BMP][TFSA]) room-temperature ionic liquid (RTIL). The adsorption of CN^? yielded single SFG and DFG bands in the range from ca. 2125 to 2135 cm^?1, exhibiting a Stark tuning of ca. 3 cm^?1 V^?1. Vibrational resonances – corresponding to modes of the RTIL coadsorbed with CN^?, were found in the range from ca. 1200 to 1500 cm^?1. The study of the double-layer structure was complemented by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements, from which the differential double-layer capacity (C_DL) was estimated.     

Vapour pressure of C60 by a transpiration method using a horizontal thermobalance

A horizontal thermal analysis system was adopted for the measurement of vapour pressure of C₆₀ using the vapour transport technique. The experimental precautions taken in order to ensure measurement of equilibrium vapour pressure by the transpiration method are described. The equilibrium nature of these measurements was ensured by the existence of plateau regions in the isothermal plots of apparent vapour pressure as a function of flow rate of the carrier gas. To verify the applicability of this TG based transpiration method, vapour pressure of CsI was measured to be log(p/Pa)=11.667±0.013−(9390±0.078)/T (K) over the range 737–874 K yielding a value of 195.6 kJ mol⁻¹ for the third-law enthalpy of sublimation, ΔH⁰_sub,298 of CsI, the value which compares well with the literature data. The vapour pressure measurements on C₆₀ over the range 789–907 K could be represented by log(p/Pa)=9.018±0.061−(7955±0.280)/T(K). Third-law treatment of the data yielded a value of 183.5±1.0 kJ mol⁻¹ for ΔH⁰_sub,298 of C₆₀ which is in good agreement with some of the other vapour pressure measurements in the literature, if subjected to third-law processing using the same set of free energy functions reliably reported in the literature.     

On the kinetics of thermal electron attachment to perfluoroethers

In this Letter we report the results of the measurements of the rate coefficients for thermal attachment to several perfluoroethers namely perfluorodiglyme (C₆F₁₄O₃), perfluorotriglyme (C₈F₁₈O₄), perfluoropolyether (CF₃–(OCF(CF₃)CF₂)_n–(OCF₂)_m–OCF₃) and perfluorocrownether ((C₂F₄O)₅). Rate coefficients were obtained under thermal conditions in the temperature range 298–378 K. The increase of the rates with temperature follows the Arrhenius law and the activation energies have been obtained from the slope of the ln(k) vs. 1/T. The respective values of the rate coefficients (at 298 K) and activation energies are as follows: 7.7 ± 1.2 × 10^?11 cm³ s^?1 (0.18 ± 0.005 eV), 6.7 ± 2.1 × 10^?11 cm³ s^?1 (0.25 ± 0.004 eV), 2.1 ± 0.2 × 10^?10 cm³ s^?1 (0.16 ± 0.010 eV), 3.1 × 10^?11 cm³ s^?1 (0.27 ± 0.003 eV) for C₆F₁₄O₃, C₈F₁₈O₄, CF₃–(OCF(CF₃)CF₂)_n–(OCF₂)_m–OCF₃ and (C₂F₄O)₅.     

ATP- and redox-induced conformational changes in the activator of the radical enzyme 2-hydroxyisocaproyl-CoA dehydratase

A [4Fe–4S]¹⁺ cluster-containing protein activates 2-hydroxyisocaproyl-CoA dehydratase by an ATP-driven electron transfer. The activator has been proposed to change its conformation by MgATP similarly to nitrogenase Fe-protein. Iron chelation by bathophenanthroline removed the reduced [4Fe–4S]¹⁺ cluster from the activator in an ATP-dependent manner (rate, v = 0.128 ± 0.004 min⁻¹; K_m = 21 ± 1 μM); with ADP no chelation was observed (v < 0.001 min⁻¹). Chelation of the oxidised [4Fe–4S]²⁺ cluster occurred faster with ADP (v = 0.34 ± 0.05 min⁻¹) than with ATP (v = 0.132 ± 0.005 min⁻¹). The data indicate that reduction of the activator and binding of ATP induce conformational changes necessary to transfer the electron to the dehydratase. Interaction of both proteins promotes ATP hydrolysis (K_m = 0.5 ± 0.1 μM).     

Thermodynamic properties,detonation characterisation and free radical of N-acetyl-3,3-dinitroazetidine

N-acetyl-3,3-dinitroazetidine (ADNAZ) is an important precursor for synthesizing new multinitroazetidine energetic compounds. Its thermal behaviour was studied under a non-isothermal condition by DSC and TG/DTG methods, the results show that there are one melting process and one endothermic decomposition process. The specific molar heat capacity (C_p,m) of ADNAZ was determined by a continuous C_p mode of micro-calorimeter and theoretical calculation, and the C_p,m of ADNAZ was 240.37 J · K⁻¹ · mol⁻¹ at T = 298.15 K. The detonation velocity (D) and detonation pressure (P) of ADNAZ were estimated using the nitrogen equivalent equation according to the experimental density, the value of D and P are (6685.83 ± 3.12) m · s⁻¹ and (18.36 ± 0.02) GPa, respectively. The free radical signals of ADNAZ were detected by electron spin resonance (ESR) technique, which is used to estimate its sensitivity.     

The standard molar enthalpy of sublimation ofη5-bis-pentamethylcyclopentadienyl iron measured with an electrically calibrated vacuum-drop sublimation microcalorimetric apparatus

A heat-flow Calvet microcalorimeter was adapted for the measurement of sublimation enthalpies by the vacuum-drop method, with samples of masses in the range 1 mg to 5 mg. The electrically calibrated apparatus was tested by determining the enthalpies of sublimation of benzoic acid and ferrocene, at T =  298.15 K. The obtained results, Δ_cr^gH_m^o(C₇H₆O₂)  =  (88.3  ±  0.5)kJ · mol ^− 1and Δ_cr^gH_m^o(C₁₀H₁₀Fe) =  (73.3  ±  0.1)kJ · mol ^− 1, are in excellent agreement with the corresponding values recommended in the literature. Subsequent application of the apparatus to the determination of the enthalpy of sublimation of η⁵-bis-pentamethylcyclopentadyenyl iron, at T =  298.15 K, led to Δ_cr^gH_m^o(C₂₀H₃₀Fe)  =  (96.8  ±  0.6)kJ · mol ^− 1.     

Dinuclear Rh(I) complex with 2,7-bis(diphenylphosphino)-1,8-naphthyridine: Synthesis,structure, and dynamic property

Reaction of [RhCl(cod)]₂ with 2,7-bis(diphenylphosphino)-1,8-naphthyridine (dpnapy) and 2,6-xylyl isocyanide (XylNC) in the presence of NH₄PF₆ afforded the dirhodium(I) complex, [Rh₂(μ-dpnapy)₂(XylNC)₄](PF₆)₂ (5), and similar procedures using [MCl₂(cod)] (M = Pt, Pd) resulted in the formation of [Pt₂(μ-dpnapy)₂(XylNC)₄](PF₆)₄ (6) and [Pd₂Cl₂(μ-dpnapy)₂(XylNC)₂](PF₆)₂ (7). Complexes 5–7 were characterized by elemental analysis, IR, UV–Vis, ¹H and ³¹P{¹H} NMR, and ESI mass spectroscopic techniques, to involve a small and rigid d⁸ {M₂(μ-dpnapy)₂} metallomacrocycle. Complex 5 readily incorporated a silver(I) ion into the macrocycle to afford [Rh₂Ag(μ-dpnapy)₂(XylNC)₄](PF₆)₃ (8) which was characterized by X-ray crystallography. The Ag(I) ion is trapped by two trans N atoms of dpnapy ligands, resulting in an asymmetric Rh–Ag⋯Rh structure, determined as a disordered model in the crystal structure, and however, in a CH₂Cl₂ solution, a dynamic interconversion of the two Ag-trapped sites was observed with low-temperature NMR studies, which was further supported by DFT molecular orbital calculations. When an acetonitrile solution of complex 5 was treated over a droplet of mercury(0), the polymeric compound formulated as {[Rh(μ-dpnapy)(XylNC)₂](PF₆)}_n (9) was isolated as yellow single crystals, which were revealed by X-ray crystallography to consist of C₆ helical rods along c axis with a pitch of 33.5 Å (rise of unit = 5.6 Å) and a diameter of 20.64 Å.     

Piperazinium dihydrogen phosphate,C4H12N2(H2PO4)2: Synthesis, 31P CP/MAS NMR,structural and thermal investigations

A new piperazinium dihydrogen orthophosphate, C₄H₁₂N₂(H₂PO₄)₂ was discovered and characterized by combining information from X-ray diffraction, ³¹P CP/MAS NMR and thermal analysis (TG/DTA). The compound C₄H₁₂N₂(HPO₄)·H₂O, was also studied in order to compare these two similar materials. The hydrothermal stability is investigated for the system: 1.0 C₄H₁₀N₂: n H₃PO₄: 55–60 H₂O, 0.5 < n < 3. The reaction mixtures with pH in the range 1.6–8.4 were placed at a fixed temperature in the range 20–180 °C for ca. 5 days. C₄H₁₂N₂(H₂PO₄)₂ was obtained when n > ca. 2. A crystal of piperazinium dihydrogen phosphate, C₄H₁₂N₂(H₂PO₄)₂ was structurally investigated using X-ray diffraction: triclinic, space group $P\overline{1}$, a = 7.023(2), b = 7.750(3), c = 12.203(4) Å, α = 84.668(7), β = 81.532(7) and γ = 63.174(6)°, V = 586.0(4) Å³ and Z = 2. The reactivity of C₄H₁₂N₂(H₂PO₄)₂ was investigated by systematic solvothermal syntheses.     

Molar heat capacity and thermodynamic properties of 1-cyclohexene-1,2-dicarboxylic anhydride [C8H8O3]

The molar heat capacity C_p,m of 1-cyclohexene-1,2-dicarboxylic anhydride was measured in the temperature range from T=(80 to 360) K with a small sample automated adiabatic calorimeter. The melting point T_m, the molar enthalpy Δ_fusH_m and the entropy Δ_fusS_m of fusion for the compound were determined to be (343.46 ± 0.24) K, (11.88 ± 0.02) kJ · mol⁻¹ and (34.60 ± 0.06) J · K⁻¹ · mol⁻¹, respectively. The thermodynamic functions [H_(T)−H_(298.15)] and [S_(T)−S_(298.15)] were derived in the temperature range from T=(80 to 360) K with temperature interval of 5 K. The mass fraction purity of the sample used in the adiabatic calorimetric study was determined to be 0.9928 by using the fractional melting technique. The thermal stability of the compound was investigated by differential scanning calorimeter (DSC) and thermogravimetric (TG) technique, and the process of the mass-loss of the sample was due to the evaporation, instead of its thermal decomposition.     

The thermodynamic properties of DyBr3(s) and DyI3(s) from T=5 K to their melting temperatures

Low-temperature calorimetric measurements have been performed on DyBr₃(s) in the temperature range (5.5 to 420 K ) and on DyI₃(s) from T=4 K to T=420 K. The data reveal enhanced heat capacities below T=10 K, consisting of a magnetic and an electronic contribution. From the experimental data on DyBr₃(s) a C⁰_p,m (298.15 K) of (102.2±0.2) J·K⁻¹·mol⁻¹ and a value for {S⁰_m (298.15 K) − S⁰_m (5.5 K)} of (205.5±0.5) J·K⁻¹·mol⁻¹, have been obtained. For DyI₃(s), {S⁰_m (298.15 K) − S⁰_m (4 K)} and C⁰_p,m (298.15 K) have been determined as (226.9±0.5) J·K⁻¹·mol⁻¹ and (103.4±0.2) J·K⁻¹·mol⁻¹, respectively. The values for {S⁰_m (5.5 K) − S⁰_m (0)} for DyBr₃(s) and {S⁰_m (4 K) − S⁰_m (0)} for DyI₃(s) have been calculated, giving S⁰_m (298.15 K)=(212.3±0.9) J·K⁻¹·mol⁻¹ in case of DyBr₃(s) and S⁰_m (298.15 K) =(233.1±0.7) J·K⁻¹·mol⁻¹ for DyI₃(s). The high-temperature enthalpy increment has been measured for DyBr₃(s) in the temperature range (525 to 799 K) and for DyI₃(s) in the temperature range (525 to 627 K). From the results obtained and enthalpies of formation from the literature, thermodynamic functions for DyBr₃(s) and DyI₃(s) have been calculated from T→0 to their melting temperatures at 1151.0 K and 1251.5 K, respectively.     

Thermodynamic properties of soddyite from solubility and calorimetry measurements

The release of uranium from geologic nuclear waste repositories under oxidizing conditions can only be modeled if the thermodynamic properties of the secondary uranyl minerals that form in the repository setting are known. Toward this end, we synthesized soddyite ((UO₂)₂(SiO₄)(H₂O)₂), and performed solubility measurements from both undersaturation and supersaturation. The solubility measurements rigorously constrain the value of the solubility product of synthetic soddyite, and consequently its standard-state Gibbs free energy of formation. The log solubility product (lg K_sp) with its error (1σ) is (6.43 + 0.20/−0.37), and the standard-state Gibbs free energy of formation is (−3652.2 ± 4.2 (2σ)) kJ mol⁻¹. High-temperature drop solution calorimetry was conducted, yielding a calculated standard-state enthalpy of formation of soddyite of (−4045.4 ± 4.9 (2σ)) kJ · mol⁻¹. The standard-state Gibbs free energy and enthalpy of formation yield a calculated standard-state entropy of formation of soddyite of (−1318.7 ± 21.7 (2σ)) J · mol⁻¹ · K⁻¹. The measurements and associated thermodynamic calculations not only describe the T = 298 K stability and solubility of soddyite, but they also can be used in predictions of repository performance through extrapolation of these properties to repository temperatures.     

The molar enthalpies of solution and vapour pressures of saturated aqueous solutions of some cesium salts

Vapour pressures of water over saturated solutions of cesium chloride, cesium bromide, cesium nitrate, cesium sulfate, cesium formate, and cesium oxalate were determined as a function of temperature. These vapour pressures were used to evaluate the water activities, osmotic coefficients and molar enthalpies of vapourization. Molar enthalpies of solution of cesium chloride, Δ_solH_m(T = 295.73 K; m = 0.0622 mol · kg⁻¹) = (17.83 ± 0.50) kJ · mol⁻¹; cesium bromide, Δ_solH_m(T = 293.99 K; m = 0.0238 mol · kg⁻¹) = (26.91 ± 0.59) kJ · mol⁻¹; cesium nitrate, Δ_solH_m(T = 294.68 K; m = 0.0258 mol · kg⁻¹) = (37.1 ± 2.3) kJ · mol⁻¹; cesium sulfate, Δ_solH_m(T = 296.43 K; m = 0.0284 mol · kg⁻¹) = (16.94 ± 0.43) kJ · mol⁻¹; cesium formate, Δ_solH_m(T = 295.64 K; m = 0.0283 mol · kg⁻¹) = (11.10 ± 0.26) kJ · mol⁻¹ and Δ_solH_m(T = 292.64 K; m = 0.0577 mol · kg⁻¹) = (11.56 ± 0.56) kJ · mol⁻¹; and cesium oxalate, Δ_solH_m(T = 291.34 K; m = 0.0143 mol · kg⁻¹) = (22.07 ± 0.16) kJ · mol⁻¹ were determined calorimetrically. The purity of the chemicals was generally greater than 0.99 mass fraction, except for HCOOCs and (COOCs)₂ where purities were approximately 0.95 and 0.97 mass fraction, respectively. The uncertainties are one standard deviations.     

New thioether–dithiolate complexes of Cp1Ir and some reactivity features

The reaction of [Cp1IrCl₂]₂ (Cp* = η⁵ − C₅Me₅) with the tridentate 3-thiapentane-1,5-dithiolate ligand, S(CH₂CH₂S⁻)₂ (tpdt), led to the formation of [Cp1Ir(η³ − tpdt)] (1) in 81% isolated yield. Subsequent reactions of 1 with [Cp1IrCl₂]₂ in 2:1 and 1:1 molar equiv ratios resulted in the formation of [Cp1Ir(μ − η²:η³ − tpdt)Cp1IrCl][PF₆] (2) and [Cp1Irμ − η²:η³ − tpdt)Cp1IrCl][Cp1IrCl₃] (3) in 86 and 79% yields, respectively, based on 1, whereas the reactions of 1 with [(COD)IrCl]₂ (COD = 1,5-cyclooctadiene) in 2:1 and 1:1 molar equiv ratios resulted in the formation of the homo-bimetallic derivatives Cp1Ir(μ − η¹:η³ − tpdt)(COD)IrCl (4) (92% yield) and [Cp1Ir(μ − η²:η³ − tpdt)(COD)Ir] [(COD)IrCl₂] (5) (82% yield). Reactions between 1 and [(COD)RhCl]₂, yielded the hetero-bimetallic derivatives Cp1Ir(μ − η¹:η³ − tpdt)(COD)RhCl (6) and [Cp1Ir(μ − η²:η³ − tpdt)(COD)Rh][(COD)RhCl₂] (7), in 92 and 93% yields, respectively. The reaction of 1 with methyl iodide gave mono-methylated derivative [Cp1Ir(η³-C₄H₈S₃Me)]I (8) (93% yield). All these compounds have been comprehensively characterized.