114490-26-5Relevant articles and documents
A new sulfur-bridged Ir(I)-Ir(I) compound and its conversion to a compound containing a metal-metal bond. Crystal structures of Ir2(SPh)2(COD)2 and Ir2Cl2(μ2-SPh)2(COD)2
Cotton, F. Albert,Lahuerta, Pascual,Latorre, Julio,Sanaú, Mercedes,Solana, Isabel,Schwotzer, Willi
, p. 2131 - 2135 (2008/10/08)
The thiolato-bridged dinuclear compound Ir2(SPh)2(COD)2 (1) was obtained from the alkoxide-bridged analogue by ligand exchange. 1 crystallizes in the space group P21/c with a = 11.249 (6) ?, b = 11.564 (5) ?, c = 19.568 (10) ?, β = 100.28 (5)°, and Z = 4. The dinuclear molecule consists of Ir atoms with square-planar coordination sharing a S?S edge. The Ir?Ir separation of 3.181 (1) ? agrees with the assumed absence of a bond. The dinuclear compound is nonrigid in solution. Upon oxidative addition of halogens (Br2, I2), the dimeric M-M-bonded compounds of Ir(II), Ir2X2(μ2-SPh)2(COD)2, are obtained. Alternatively, the Br and I derivatives can be prepared by electrochemical reduction of Ir2(μ2-X)2X2(COD)2 (X = Br, I), followed by oxidative addition of PhSSPh. The chloro analogue, 2, was prepared by oxidative addition of PhSSPh to Ir2Cl2(COD)2 and was structurally characterized. It crystallizes in the space group P1 with a = 8.370 (2) ?, b = 12.155 (1) ?, c = 13.184 (2) ?, α = 94.33 (1)°, β = 97.63 (2)°, γ = 96.47 (1)°, and Z = 2. The molecules are M-M-bonded dimers consisting of edge-sharing square pyramids. The Ir-Ir bond length is 2.800 (1) ?. The 13C and 1H NMR spectra indicate that the solid-state structure is retained in solution. The phenyl rings of the thiolate bridges exhibit a syn relationship with respect to the four-membered [IrS]2 core, and the mean planes of the phenyl rings are approximately perpendicular to the Ir-Ir vector. The average Ir-S bond length is 2.345 (2) ?. Other important bond lengths and angles are given in Table III.
