136576-31-3Relevant academic research and scientific papers
Multiply bonded octahalodiosmate(III) anions. 5. Cleavage of the electron-rich Os≡Os bond by carbon monoxide and isocyanide ligands
Johnson, Thomas W.,Tetrick, Stephen M.,Fanwick, Phillip E.,Walton, Richard A.
, p. 4146 - 4152 (2008/10/08)
The triply bonded diosmium(III) complexes (n-Bu4N)2Os2X8 (X = Cl, Br) react with isocyanide ligands RNC (R = CHMe2, CMe3, xylyl, mesityl) in ethanol at room temperature to afford the 17-electron, paramagnetic, mononuclear osmium(III) species (n-Bu4N)[OsX4(CNR)2] in very high yield. A similar reaction with carbon monoxide in hot ethanol gives (n-Bu4N)[OsX4(CO)(EtOH)], which upon reaction with other monodentate donors loses ethanol and forms (n-Bu4N)[OsX4(CO)L], where L = DMSO, THF, CH3CN, py, PPh3, PEt3, or xylNC. The spectroscopic and electrochemical properties of these complexes, as well as single-crystal X-ray structural studies on (n-Bu4N)[OsCl4(CNxyl)2] and a crystal of composition (n-Bu4N)[OsCl4-xBrx(CO)(DMSO)] (x ? 1.32) have shown that the anions possess trans-[OsX4(CNR)2]- and trans-[OsX4(CO)L]- geometries. Crystal data for (n-Bu4N)[OsCl4(CNxyl)2] at 20°C are as follows: monoclinic space group P21/n, a = 11.6698 (7) A?, b = 31.786 (3) A?, c = 21.484 (2) A?, β = 102.111 (5)°, V = 7791 (2) A?3, and Z = 2. The structure was refined to R = 0.047 (Rw = 0.056) for 4658 data with I > 3.0σ(I). Crystal data for (n-Bu4N)[OsCl2.68Br1.32(CO)(DMSO)] at 20°C: triclinic space group P1, a = 9.026 (2) A?, b = 10.479 (1) A?, c = 16.328 (2) A?, α = 95.35 (1)°, β = 94.68 (2)°, γ = 110.63 (1)°, V = 1428.2 (8) A?3, and Z = 2. The structure was refined to R = 0.041 (Rw = 0.062) for 3188 data with I > 3.0σ(I).
