87584-88-1

Upstream product

• 2314-97-8 iodotrifluoromethane 
• 556-56-9 allyl iodid 
• 74-88-4 methyl iodide 
• 32354-35-1 C₆H₅ORh(CO)(P(C₆H₅)3)2 
• 15318-33-9 trans-carbonyl(chloro)bis(triphenylphosphine)rhodium(I) 
• 139-02-6 sodium phenoxide 
• 104710-85-2 Rh(CO)(NCOC₂H₄CO)(P(C₆H₅)3)2 
• 14056-79-2 bromocarbonylbis(triphenylphosphine)rhodium(I) 
• 7681-82-5 sodium iodide 
• 89579-40-8 Rh(P(C₆H₅)3)2(COCH₃)I₂ 
• 15318-33-9 chlorocarbonylbis(triphenylphosphine)rhodium(I) 
• 10034-85-2 hydrogen iodide 
• 44769-94-0 iodocarbonyl rhodium anion 
• 7446-09-5 sulfur dioxide 

Downstream Products

• 87559-51-1 trans-[RhI(CO)(O₂)(PPh₃)2] 
• 101075-58-5 (triphos)Rh(CO)(I) 

Relevant academic research and scientific papers

Hydroxycarbonylation of alkenes with formic acid using a rhodium iodide complex and alkyl ammonium iodide

Hydroxycarbonylation of alkenes using formic acid (HCOOH) is ideal for the synthesis of various carboxylic acids as a means to develop a sustainable reaction system with lower environmental impact. In this study, we developed a new catalytic system for hydroxycarbonylation of alkenes with HCOOH using a Vaska-type Rh complex with an iodide ligand, RhI(CO)(PPh3)2(1), as the catalyst, and a quaternary ammonium iodide salt as the promoter for the catalyst. In comparison with similar reaction systems using Rh catalysts, our reaction system is safer and more environmentally friendly since it does not require high-pressure conditions, explosive gases, or environmentally unfriendly CH3I and extra PPh3promoters. In addition, we also experimentally clarified that the catalytic reaction proceedsviaRhHI2(CO)(PPh3)2(2), which is formed by the reaction of1with a quaternary ammonium iodide salt andp-TsOH. Furthermore, the Rh(iii) complex2can catalyze hydroxycarbonylation of alkenes with HCOOH without any promoters.

Rhodium-catalyzed dimerization of terminal alkynes assisted by MeI

Dimerization of terminal arylalkynes at ambient temperature catalyzed by Rh(CO)PPh3)2-Cl (2) in the presence of MeI leads to formation of enyne with high conversion and high regio- and stereoselectivity. A rhodium intermediate captured from oxidative addition of Mel was used for dimerization of alkyne with selectivity controlled by the use of solvents. In aprotic solvent (such as acetone, CH2Cl2, or THF) dimerization of terminal alkynes HC≡C(p-C6H4X) (1, X = H, a; NO2) b; C(O)H, c; Me, d; CN, e; NMe2, f; CF 3, g, F, h; Br, i; I, j) leads to the (E)-1,4-disubstituted enynes 6 (a-k) in high selectivity. However, when MeOH is used as a solvent, the dimerization of 1-arylalkynes containing an electron-withdrawing group affords selectively the (Z)-1,4-disubstituted enyne 8. Requirement of the presence of Mel for this conversion indicates that the process presumably involves initially a six-coordinated rhodium methylacetylide intermediate. Oxidative addition of ICH2CN to 2 yielded the catalytically inactive six-coordinated complex Rh(CO)(PPh3) 2(C≡CPh)(I)(CH2-CN) (5a). The analogous complex 5b with a p-nitro group on the phenyl acetylide ligand is characterized by X-ray diffraction analysis.

Reaction of Sulfur Dioxide with Halocarbonyls of Rhodium and Iridium

The reactions of SO2 with halocarbonyl anions of rhodium and iridium [M(CO)2X2](1-) (M = Rh, Ir; X = Cl, Br, I), were studied. Addition of neutral ligands, Ph3E (E = P, As, Sb) or pyridine, to the SO2 treated halocarbonyl solution resulted in the formation of various complexes according to the nature of the precursor complex and the ligand. The obtained complexes are formulated as Rh(CO)(SO2)(Ph3As)2Cl, [Rh(py)2(SO2)Cl].2H2O, Rh(CO)(SO2)(Ph3P)2Br, Rh2(CO)2(SO2)(Ph3Sb)2Br2, Rh(py)2(SO2)2I(C2H5OH), Rh(SO2)3I(C2H5OH) and Rh2(CO)2(SO2)3(Ph3Sb)2I2, Ir(SO2)2Br(H2O)2, [Ir(SO2)4(Ph3Sb)Br].6H2O, Ir(SO2)I(H2O)2 and [Ir(SO2)2(Ph3As)I3].4H2O. All complexes obtained have been characterized by physico-chemical methods.

Carbon-oxygen bond formation on rhodium centers. Synthesis, characterization, crystal structure, and reactions of trans-PhORh(CO)(PPh3)2

The synthesis of a rhodium phenoxide is reported. The complex trans-PhORh(CO)(PPh3)2 crystallizes in the centrosymmetric monoclinic space group P21/c with a = 15.794 (3) ?, b = 11.449 (2) ?, c = 20.025 (3) ?, β = 100.220 (13)°, V = 3562 (1) ?3, and Z = 4. Diffraction data (Mo Kα, 2θ = 4.5-50.0°) were collected with a Syntex P21 diffractometer, and the structure was refined to RF = 2.8% for 5293 reflections. The structure is isomorphous with the iridium analogue. Important dimensions include Rh-P = 2.337 (1)-2.357 (1) ?, Rh-CO = 1.801 (3) ?, Rh-OPh = 2.044 (2) ?, and Rh-O-C(phenoxide) = 125.52 (19)°. This complex reacts with Ph2CHC(O)Cl to give the ester Ph2CHC(O)OPh and with MeI to give anisole, PhOMe. The formation of anisole from the rhodium phenoxide is in contrast to the failure to eliminate ethers from similar iridium complexes and is consistent with the known preference for elimination from second-row (rather than third-row) transition-metal complexes.

Novel Halogen Exchange Reactions between Halosilanes and Rh(I) or Ir(I) Complexes

Vaska-type complexes such as MCl(CO)L2 (M=Rh or Ir, L= tertiary phosphine) or the Wilkinson complex RhCl(PPh3)3 underwent halogen exchange reactions with halosilanes Me3SiX (X=Br, I) to give MX(CO)L2 or RhX(PPh3)3 respectively with the formation of Me3SiC

Transition Metal Complexes with Terminal or Bridging Imidato(1-) Ligands. X-Ray Crystal Structures of trans- and 2>*CH2Cl2, Spectroscopic Studies of , and the Nature of the Metal-Nitrog...

The reaction of with the thallium(I) salt of succinimide yields the novel succinimidato(1-) complex .The imide-derived ligand is found to behave as a pseudo-halogen in terms of its ?-acceptor and ?-donor properties by 'Graham' analysis of i.r. spectroscopic data.Mononuclear arylpalladium complexes, trans- , and related carbonyl-rhodium and -iridium complexes, trans-, may be synthesised by reaction of the corresponding chloro-complexes with succinimide, phthalimide, or tetrafluorosuccinimide.The structure of trans- has been established crystallographically (Ir-N 2.09 Angstroem).Binuclear arylpalladium complexes containing halide or acetate bridges react with imides in the presence of base to give complexes in which the imidato(1-) ligand adopts a novel bridging co-ordination mode, via nitrogen and one of the carbonyl oxygens.The structure of one complex of this type, 2>*CH2Cl2, has been confirmed crystallographically.

Acid-base chemistry of the methylrhodium(III) derivative CH3RhI2(PPh3)2

Reaction of excess methyl iodide with the 14-electron Rh(I) salt (Ph3P)3Rh+HC(SO2CF3) 2- produces green CH3RhI2(PPh3)2, λmax 500 and 610 nm. Crystal data: monoclinic (centric), C2/c, a = 23.982 (5) A?, b = 9.828 (3) A?, c = 16.063 (6) A?, β = 114.73 (3)°, Z = 4, and V = 3439 (4) A?3. The structure, solved by using 2618 reflections for which Fo2 > 1.0 σ(Fo2), converged at R = 0.022 and Rw = 0.034. The coordination geometry of rhodium(III) is flattened square pyramidal with a C2 axis through rhodium and the methyl carbon. The metal is displaced 0.25 A? toward the apical methyl group from the least-squares plane containing two trans iodines and two trans phosphorus atoms, which comprise the base of the pyramid. Important bond distances are d(Rh-C) = 2.06 (1) A?, d(Rh-I) = 2.635 (1) A?, and d(Rh-P) = 2.365 (2) A?. Ch3RhI2(PPh3)2 has an extensive acid-base chemistry. It is converted by excess carbon monoxide to cis- and trans-CH3CORhI2(PPh3)2CO from which reversible dissociation of the terminal carbonyl ligand leads to CH3CORhI2(PPh3)2. This acetylrhodium(III) compound decomposes by reductive elimination of methyl iodide to form (Ph3P)2Rh(LO)I. Trimethylphosphine and trimethyl phosphite displace triphenylphosphine to yield mer-CH3RhI2L3 (L = (CH3O)3P, (CH3)3P). Migratory insertion of sulfur dioxide into the CH3 bond provides CH3SO2RhI2(PPh3)2.

THE PREPARATION OF cis- AND trans- (Ar = ARYL) AND THEIR READY DISSOCIATION IN SOLUTION

Attempts to prepare complexes have shown that when X=I these complexes are far less stable than the well-known .The bromo complexes (Ar=C6H5, p-EtC6H4) can be prepared by simple halide exchange from their respective chloro complexes.However a similar attempt to prepare the iodo complexes was frustrated by dissociative equilibria; in the absence of oxygen dimers were formed, whereas in the presence of oxygen polymeric oxygen complexes were formed.The ease of dissociation of phosphine can be attributed to the greater steric crowding in the iodo complexes than in the chloro and bromo complexes.The complex could only be obtained in the presence of excess PPh3, which inhibits the dissociation.The identification of this monomer was further complicated by the previously unnoticed presence of both cis and trans isomers in the solid state.

REACTIONS INVOLVING TRANSITION METALS. XVII. REACTION OF ORGANIC HALOGEN COMPOUNDS WITH 2 AND 2 (S = CH2Cl2, THF)

The complexes 2 and 2 (S=CH2Cl2, THF) have been shown to react with CXCl3 (X=Cl, H) to form with generation of both dichlorocarbene and trichloromethyl radical.Reaction of 2 with CF3I, allyl- and benzyl-halides takes a different course giving organic coupling products and .The THF solvate complex also causes coupling of gem-dihalides, and dehalogenation of vic-dihalides to produce alkenes.Possible mechanisms for these reactions are discussed.

Reactions involving Transition Metals. Part 15. Reactions of Alkyl an Acyl-peroxy-anions with (1+) (M= Ir or Rh)

The title compounds react with peroxycarboxylic acids RCO3H in the presence of NEt3 to give the compounds (L = PPh3), which, with MeI, give and (R = C6H4Cl-m, Ph, or Me).Reaction between NaO2COR' (R' = C6H4Cl-m) and (1+) affords an inseparable mixture of , , and ; under similar conditions the rhodium analogue gives a mixture of and .Reactions between NaO2But and either (1+) or give only .