864513-47-3

Upstream product

• 201230-82-2 carbon monoxide 
• 865-47-4 potassium tert-butylate 
• 864513-36-0 [RhIr(CH3)2(CO)3(μ-Ph2PCH2PPh2)2] 

Downstream Products

• 143171-99-7 {RhIr(CH₃)(CO)3((C₆H₅)2PCH₂P(C₆H₅)2)2}⁽¹⁺⁾*CF₃SO₃^(1-)={RhIr(CH₃)(CO)3((C₆H₅)2PCH₂P(C₆H₅)2)2}{CF₃SO₃} 
• 1257862-58-0 [RhIr(H)(SiMe2H)(CO)3(κ1-dppm)(μ-SiMe2)(dppm)] 
• 173538-72-2 [RhIr(CO)2(μ-C(CH3)=NtBu)(Ph2PCH2PPh2)2]OSO2CF3 

Relevant academic research and scientific papers

Multiple silicon-hydrogen bond activations at adjacent rhodium and iridium centers

The reaction of 1 equiv of primary silanes, SiH3R (R = Ph, Mes), with [RhIr(CO)3(dppm)2] yields mono(silylene)-bridged complexes of the type [RhIr(H)2(CO)2(μ-SiHR)(dppm) 2] (R = Ph or Mes),

Dialkyl and trialkyl heterobinuclear complexes of rhodium and iridium: Models for adjacent-metal involvement in bimetallic catalysts

The heterobinuclear dialkyl complexes [RhIr(R)2(μ-CO)(dppm) 2] (dppm = μ-Ph2PCH2PPh2; R = CH3 (2), CH2Ph (3)) have been prepared. Both A-frame-like compounds have one alkyl group terminally bound to each metal and a bridging carbonyl ligand. Some subsequent reactivity studies of 2 are reported. Reaction of 2 with CO yields [RhIr(CO)3(dppm)2] and acetone. If this reaction is monitored at low temperature by NMR spectroscopy, the dicarbonyl species [RhIr(CH3)2(CO)2(dppm)2] (4) is first observed, followed by [RhIr(CH3)2(CO) 3(dppm)2] (5). In both products, both methyl groups are bound to Ir. Warming to ambient temperature under CO yields acetone and [RhIr(CO)3(dppm)2]. Crossover experiments suggest that acetone arises primarily from an intramolecular process. We propose that migratory insertion of a CO and a methyl group occurs on Ir; presumably reductive elimination also occurs from this metal. Compound 2 reacts with H 2 at -78°C to yield [RhIrH(CH3)2(μ-H) (μ-CO)(dppm)2] (6), in which one methyl group is bound to Rh while the other, together with a hydride ligand, is terminally bound to Ir. This latter species reacts with CO at 0°C to yield [RhIrH-(C(O)CH 3)(CH3)(μ-H)(μ-CO)(dppm)2] (7), in which migratory insertion involving CO and the Rh-bound methyl group has yielded a Rh-bound acetyl group. At ambient temperature, under an atmosphere of CO, [RhIr(CO)3(dppm)2] is formed, together with acetaldehyde and methane. Crossover experiments support a predominantly intramolecular process for acetaldehyde formation but are equivocal on the formation of methane. Compound 2 oxidatively adds CH3I or n-C4H 9I, yielding [RhIr(CH3)2(R)(μ-I)(μ-CO) (dppm)2] (R = CH3, N-C4H9), in which the added alkyl group in each case is bound to Ir. The N-butyl product reacts with CO to yield [RhIr(n-C4H9)(CH3) 2(μ-CO)2(dppm)2][I], in which the n-butyl group has migrated to Rh. A similar product, [RhIr(CH3) 3(μ-CO)2(dppm)2][CF3SO 3], is obtained in the reaction of 2 with methyl triflate in the presence of CO.

Diphosphine-bridged heterobimetallic hydride and carbonyl complexes of rhodium and iridium. Structure of [RhIr(CO)3(Ph2PCH2PPh2) 2], a complex containing an Ir(-I)→Rh(I) dative bond

The reaction of [RhIrCl2(CO)2(dppm)2] (dppm = Ph2PCH2PPh2) with NaBH4 under CO gives [RhIr(CO)3(dppm)2] (1), while under H2 the product is [RhIr(H)(CO)2(μ-H)(dppm)2] (2). The former is convertible to the latter via reaction with H2, while the reverse process proceeds under CO atmosphere. Addition of 1 equiv of HBF4·OEt2 to 1 yields [RhIr(CO)3(μ-H)(dppm)2][BF4] (3) and addition of a second equivalent leads to [RhIr(CO)3(μ-H)2(dppm)2][BF 4]2 (4); both protonations are reversible. Protonation of 2 produces [RhIr(H)(CO)2(μ-H)2(dppm)2][BF4] (5). Like their neutral precursors, the protonated tricarbonyl and trihydride complexes may be interconverted via the appropriate hydrogenation or carbonylation processes. An X-ray structural determination of [RhIr(CO)3(dppm)3] shows it to have a non-A-frame structure, with one of the two carbonyls attached to Ir oriented toward Rh in what might be considered a weakly semibridging manner; furthermore, the phosphine groups on Ir have a cis arrangement with a P-Ir-P angle of 104.95 (7)°. The rhodium center is square planar as expected for a Rh(I) formulation, while the geometry about iridium is a distorted tetrahedron (if the Rh-Ir bond is omitted) suggesting an Ir(-I) formulation. As such the Ir(CO)2P2- moiety can be considered as a pseudohalide, bound via a dative Ir→Rh bond. This compound crystallizes in the monoclinic space group P21/c with a = 20.296 (4) A?, b = 12.190 (7) A?, c = 19.064 (7) A?, β = 95.11 (2)°, and Z = 4. The structure was refined to R = 0.047 and Rw = 0.053 on the basis of 5208 unique observed reflections and 559 parameters varied.