15692-64-5Relevant academic research and scientific papers
Coordination of sulfur dioxide to iridium(I) centers. Sulfur dioxide insertion into a methoxo-metal bond: Crystal and molecular structure of carbonyl(methyl sulfito)(sulfur dioxide)bis(triphenylphosphine)iridium-hemitoluene, the first structurally characterized example of a transition metal complex containing an O-coordinated methyl sulfito ligand
Randall, Sherri L.,Miller, Cynthia A.,Janik, Thomas S.,Churchill, Melvyn Rowen,Atwood, Jim D.
, p. 141 - 147 (2008/10/08)
Reactions of SO2 with iridium(I) complexes have been examined. For trans-Ir(CO)L2X (L = PPh3, P(p-tolyl)3, PCy3; X = Cl, Br, Me), equilibrium constants for SO2 binding have been evaluated. The binding of SO2 is as a Lewis acid and is enhanced by electron-donating groups on the iridium. Increasing the size of the phosphine reduces the equilibrium constant for SO2 binding. Reactions of SO2 with the hydroxo or alkoxo complexes Ir(CO)(OR)L2 (R = H, Me, t-Bu; L = PPh3, P(p-tolyl)3) result in insertion of the SO2 to form an oxygen-coordinated sulfite ligand. The sulfur center of the sulfite ligand is pyramidal and asymmetric, resulting in a second-order 31P NMR spectrum at low temperature. A further rearrangement of the oxygen-coordinated sulfite ligand to the sulfur-coordinated occurs in solution. For R = H, further decomposition of the HSO3- ligand occurs. The products of each reaction are characterized by infrared and 1H and 31P NMR spectroscopy. The product of SO2 insertion into the iridium-methoxo bond, Ir(CO) (OS(O)OMe)(SO2) (PPh3)2, is also characterized by X-ray crystallography. The complex Ir(CO)[OS(O)OMe](SO2)(PPh3)2 crystallizes from toluene as the hemitoluene solvate, Ir(CO)[OS(O)OMe](SO2)(PPh3) 2·0.5(toluene), in the centrosymmetric triclinic space group P1 (No. 2) with a = 10.972(5) A?, b = 11.658(4) A?, c = 18.020(11) A?, α = 82.73(4)°, β = 77.76(4)°, γ = 63.25(3)°, V = 2007.5(17) A?3, and Z = 2. The structure was solved and refined to R = 3.05% and Rw = 3.58% for all 5280 reflections with 2θ w = 3.23% for those 4502 reflections with Fo > 6σ(Fo). The iridium is in a square-pyramidal coordination environment with the SO2 ligand in the apical site. Iridium-ligand bond lengths are as follows: Ir(1)-P(1) = 2.369(2) A? and Ir(1)-P(2) = 2.387(2) A? for the Ir-PPh3 groups, Ir(1)-S(1) = 2.451(2) A? for the SO2 ligand, Ir(1)-C(1) = 1.831(6) A? for the CO ligand, and Ir-O(23) = 2.080(4) A? for the OS(=O)OMe ligand. The trans-basal angles are P(1)-Ir-(1)-P(2) = 170.3(1)° and C(1)-Ir(1)-O(23) = 176.7(2)°; angles to the apical SO2 ligand are P(1)-Ir(1)-S(1) = 97.5(1)°, P(2)-Ir(1)-S(1) = 92.2(1)°, C(1)-Ir(1)-S(1) = 97.3(2)°, and O(23)-Ir(1)-S(1) = 85.8(1)°.
The coordination chemistry of iminooxosulphuranes. The osmium and iridium series (ML = OsNO,IrCO;A = O, CH2, S, NR; R = o-tolyl, p-tolyl and p-tosyl)
Herberhold, Max,Hill, Anthony F.
, p. 323 - 336 (2007/10/02)
The preparation and characterisation of the two analogous series of compounds (A = O, CH2, S, NR; R = C6H4Me-4, C6H4Me-2, SO2C6H4Me-4) and (A = O, S, NSO2C6H4Me-4) are described.A comparison of spectroscopic data for the complex supports the isolobal relationship between the molecules OSA.
Novel Synthetic Routes to Disulphur and Disulphur Monoxide Ligands: Nucleophilic Attack at Co-ordinated Imino-oxo-λ4-sulphanes
Herberhold, Max,Hill, Anthony F.
, p. 2027 - 2032 (2007/10/02)
The reactions of and with oxo-4-tosylimino-λ4-sulphane (4-MeC6H4SO2NSO) lead quantitatively to the adducts Cl(PPh3)2(4-MeC6H4SO2NSO)> = Os(NO) or Ir(CO)> which in turn are hydrolysed to the corresponding sulphur dioxide complexes Cl(PPh3)2(SO2)>.The iridium compound reacts cleanly with hydrogen sulphide to provide the disulphur monoxide complex whilst with hydrosulphide leads to the disulphur complex which may be oxidised to the corresponding S2O complex with 3-chloroperbenzoic acid.Alternatively, is accessible via the reaction of with cyclo-octasulphur.
Reaction of Vaska's complex with thionyl chloride
Vanderpool, Richard A.,Abrahamson, Harmon B.
, p. 2985 - 2989 (2008/10/08)
The title reaction has been studied by using 31P NMR spectroscopy, and the products have been identified. If thionyl chloride is in excess throughout the reaction, only IrCl2(CO)(PPh3)2(SOCl) is formed. If Vaska's complex, IrCl(CO)(PPh3)2, is present in excess at some point, a substantial amount of decomposition is observed, some of it irreversible. The decomposition is due to attack of the reactive S(O)Cl ligand by Vaska's complex. One of the side products, IrCl(CO)(PPh3)2(SO2), displays a reversible exchange reaction in the presence of free Vaska's complex. Thermodynamic parameters for the exchange have been calculated from variable-temperature 31P NMR data: ΔG? = 40 ± 8 kJ mol-1, ΔH? = 74 ± 5 kJ mol-1, ΔS? = 113 ± 20 J K-1 mol-1. These values are consistent with a dissociated intermediate in the exchange.
