90553-00-7Relevant academic research and scientific papers
The nature of the low-lying excited states of bridged rhodium(I) and iridium(I) binuclear complexes
Kenney, M. Inga S.,Kenney III, John W.,Crosby, Glenn A.
, p. 230 - 234 (1986)
Electronic absorption and luminescence measurements on the four binuclear systems [Rh(CO)Cl(dppm)]2, [Rh(CO)Cl(dam)]2, [Ir(CO)Cl(dppm)]2, and [Ir(CO)Cl(dam)]2 [dppm = bis(diphenylphosphino)methane and dam = bis(
Preparation and characterization of some binuclear DPM-bridged complexes of indium and the structure of one product, [Ir2Cl2(CO)2(μ-CO)(Ph2PCH 2PPh2)2]·3C4H8O
Sutherland, Bruce R.,Cowie, Martin
, p. 2324 - 2331 (2008/10/08)
The reaction of bis(diphenylphosphino)methane (DPM) with [IrCl(C8H14)2]2 under CO yields the binuclear complex [Ir2Cl(CO)3(μ-CO)(DPM)2][Cl], and from this the BPh4- and BF4- salts can be readily prepared. Carbonyl loss from the chloro salt first yields two isomers of [Ir2Cl2(CO)2(μ-CO)(DPM)2] and finally trans-[IrCl(CO)(DPM)]2, whereas CO loss from the BPh4- and BF4- salts gives [Ir2(CO)2(μ-Cl)(μ-CO)(DPM)2]+ with the corresponding anion. The dicarbonyl A-frame [Ir2(CO)2(μ-Cl)(DPM)2]+ cannot readily be obtained via CO loss from the corresponding cationic tricarbonyl species but is easily obtained in the reaction of trans-[IrCl(CO)(DPM)]2 with 1 equiv of AgBF4. An X-ray structural determination of [Ir2Cl2(CO)2(μ-CO)(DPM)2] shows that the terminal carbonyl and chloro ligands are disordered. This disorder can be rationalized on the basis of the cocrystallization of two isomers, one in which all carbonyl groups are mutually cis (in approximately 25% abundance) and the other (75% abundance) in which the bridging carbonyl group is trans to a terminal carbonyl on one metal and to a chloro ligand on the other. These two isomers interconvert rapidly on the NMR time scale but can be discerned in infrared spectra. [Ir2Cl2(CO)2(μ-CO)(DPM)2] crystallizes with three molecules of THF in the space group P21/c with a = 22.890 (6) A?, b = 13.152 (4) A?, c = 22.129 (5) A?, β = 114.39 (3)°, and Z = 4. The structure was refined to R = 0.043 and Rw = 0.054 on the basis of 5303 unique observed reflections and 268 parameters varied.
