97487-41-7

Upstream product

• 159696-10-3 Ir2(μ-N(p-BrC6H4))(CO)2(bis(diphenylphosphino)methane)2 
• 159696-08-9 Ir2(μ-N(p-tolyl))(CO)2(bis(diphenylphosphino)methane)2 
• 66125-35-7 Ir₂Cl₂(CO)2(bis(diphenylphosphino)methane)2 
• 97487-40-6 [Ir₂(CO)4((C₆H₅)2PCH₂P(C₆H₅)2)2] 

Downstream Products

• 110026-35-2 {Ir₂(CO)4(H)((C₆H₅)2PCH₂P(C₆H₅)2)2}⁽¹⁺⁾*BF₄^(1-)={Ir₂(CO)4(H)((C₆H₅)2PCH₂P(C₆H₅)2)2}BF₄ 
• 261905-91-3 (Ir2(I)(Me)(CO)(μ-CO)(dppm)2) 
• 261905-92-4 (Ir2(I)(CH2OMe)(CO)(μ-CO)(dppm)2) 
• 147554-11-8 Ir₂(CO)3(H)((C₆H₅)2PCH₂P(C₆H₅)2)2(SeH) 

Relevant academic research and scientific papers

Iridium μ-imido/amido A-frame complexes

The reaction of Ir2Cl2(CO)2(μ-dppm)2 (dppm = bis(diphenylphosphino)methane) with 2 equiv of LiNHR yields Ir2(μ-NR)(CO)2(μ-dppm)2, 1 (R = p-tolyl, Ph, p-BrC6H4, p-NO2C6H4), or its tautomer Ir2(μ-NHR)(CO)2(μ-dppm)-(μ-dppm-H), 2 (dppm-H = bis(diphenylphosphino)methanide; R = Et, But). NMR data suggest that 1 (R = p-tolyl, Ph, p-BrC6H4) are in equilibrium with small amounts of 2 in polar solvents. An X-ray structural determination of 1 (R = p-tolyl) shows that the imido nitrogen atom links two iridium atoms at the apex of an A-frame complex. A very short N-C distance in the imido group suggests extensive N-lone pair donation to the tolyl ring. Crystals of 1 (R = p-tolyl) from benzene are tetragonal (P43) with a = 21.337(1) A?, c = 14.478(2) A?, and Z = 4. With the exception of R = p-NO2C6H4, p-BrC6H4, and Et, the complexes react with 1 equiv of CO at ambient temperature to form Ir2(CO)3(μ-dppm)2 as the major metal containing product. For R = Et, the reaction generates the unstable isocyanate complex Ir2(μ-EtNCO)(CO)2(μ-dppm)2. All of the complexes react with excess CO (2 atm) yielding Ir2(CO)4(μ-dppm)2 and amine except for the p-NO2C6H4 complex, which gives a complex mixture of products.

Hydroxy- and hydrido-bridged binuclear complexes of iridium: Synthesis, characterization, and attempts to model binuclear water-gas shift catalysts. Structure of [Ir2(CO)2(μ-OH·Cl)(Ph2PCH 2PPh2)2]

The reaction of trans-[IrCl(CO)(DPM)]2 with excess NaOH yields [Ir2(CO)2(μ-OH·Cl)(DPM)2] which upon treatment with HBF4·Et2O gives [Ir2(CO)2(μ-OH)(DPM)2][BF4]. Reaction of the former product with CO produces the binuclear Ir(0) complex [Ir2(CO)4(DPM)2] which after flushing with N2 yields [Ir2(CO)3(DPM)2]. Reaction of [Ir2(CO)2(μ-OH)(DPM)2][BF4] with CO produces [Ir2(CO)2(μ-H)(μ-CO)(DPM)2][BF 4]. This latter complex reacts with HBF4·Et2O to give [Ir2(H)(CO)2(μ-H)(μ-CO)-(DPM)2][BF 4]2 which rearranges with time yielding the isomeric complex [Ir2(H)2(CO)3(DPM)2][BF 4]2. Reaction of either of these dihydrides with CO produces [Ir2(CO)4(μ-H)2(DPM)2][BF 4]2 and [Ir2(CO)4(μ-CO)(DPM)2][BF4] 2 in the ratio 9:1, the latter product resulting from reductive elimination of H2. Refluxing [Ir2(H)2(CO)3(DPM)2][BF 4]2 in CH3CN also produces some H2 elimination and the formation of [Ir2-(CO)2(CH3CN) 2(μ-CO)(DPM)2][BF4]2. Reaction of [Ir2(CO)4(μ-CO)(DPM)2][BF4] 2 with OH- yields [Ir2-(CO)2(μ-H)(μ-CO)(DPM)2][BF 4] whereas reaction of [Ir2(CO)2(CH3CN)2(μ-CO)(DPM) 2][BF4]2 with OH- gives a mixture of this hydride and the bridging hydroxide complex [Ir2(CO)2(μ-OH)(DPM)2][BF4]. This chemistry is discussed and related to a model water-gas shift cycle. The related rhodium complex [Rh2(CO)2(μ-OH)(DPM)2]+ is shown to be a WGS catalyst precursor under mild conditions, although it seems that metal hydrides and not hydroxides are the catalytically important species. The complex [Ir2(CO)2(μ-OH·Cl)(DPM)2] crystallizes in the space group P212121 with a = 14.762 (2) A?, b = 25.583 (4) A?, c = 13.770 (3) A?, and Z = 4 and was refined to R = 0.043 and Rw = 0.065 based on 2650 unique observed reflections and 223 variables.