22569-53-5

Upstream product

• 17185-29-4 carbonylhydridetris(triphenylphosphine)rhodium(I) 
• 201230-82-2 carbon monoxide 
• 103948-62-5 trans-carbonyl(3-fluorobenzoato)bis(triphenylphosphine)rhodium 
• 1333-74-0 hydrogen 
• 603-35-0 triphenylphosphine 
• 688764-13-8 (3,3'-5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)(5-(phenyl-2-yl)-10,15,20-tris(phenyl) zinc(II) porphyrin)phosphite 
• 1036708-66-3 (μ-1,3-diphenyl-2,2-dithiolatopropane)bis(cyclooctadiene)dirhodium(I) 
• 494804-05-6 dodecacarbonyltetrarhodium⁽⁰⁾ 
• 592-41-6 1-hexene 

Relevant academic research and scientific papers

In situ high pressure FT-IR spectroscopy on alkene hydroformylation catalysed by RhH(CO)(PPh3)3 and Co2(CO) 8

Catalytic hydroformylation of olefins studied by HP FT-IR cell using RhH(CO)(PPh3)3 catalytic precursor shows a different behaviour between a terminal and an internal alkene. Different rate-determining steps have been hypothesised. Catalytic hydroformylation of olefins has been carried out in a HP FT-IR cell using RhH(CO)(PPh3)3 catalytic precursor. A different behaviour was noticed between a terminal (hex-1-ene) and an internal alkene (cyclohexene) and different rate-determining steps of the catalytic cycle have been hypothesised. The hydroformylation of hex-1-ene has also been tested in the presence of Co2(CO)8 as catalyst. In this case, only the catalytic precursor is evidenced by HP FT-IR. Finally, the influence of an additional gas (helium, nitrogen or argon) in the reaction medium was evaluated: a high pressure of argon or nitrogen affects the initial rate of the reaction as shown by a decrease of the rate of the aldehyde formation.

Carbon Dioxide Activation; Formation of trans-(Ph3P)2Rh(CO)(OCO2H) in the Reaction of CO2 with HRh(CO)(PPh3)3-CO and the Determination of its Structure by X-Ray Crystallography

The intermediate produced from the interaction of HRh(CO)(PPh3)3 with CO reacts with carbon dioxide to yield a novel hydrogencarbonate complex, trans-(Ph3P)2Rh(CO)(OCO2H) (1), whose structure has been established by X-ray crystallography; (1) undergoes reversible loss of CO2.

In Situ High-Pressure 31P{1H} NMR Studies of the Hydroformylation of 1-Hexene by RhH(CO)(PPh3)3

The hydroformylation of 1-hexene with syngas (40 bar of 1:1 CO/H2) in the presence of the catalyst precursor RhH(CO)(PPh3)3 has been studied by high-pressure NMR spectroscopy in a 10 mm sapphire tube equipped with a Ti-alloy valve. Except for RhH(CO)2(PPh3)2, no direct observation of labile intermediates involved in the catalytic cycle has been detected; however as many as four rhodium resting states have been seen, and some factors controlling their formation/interconversion/inhibition have been identified. The information gathered from this in situ investigation is particularly relevant to a better understanding of the inhibiting action of the CO pressure as well as the positive action of PPh3 addition.

Synthesis and characterisation of two novel Rh(I) carbene complexes: Crystal structure of [Rh(acac)(CO)(L1)]

The [Rh(acac)(CO)(L)] (acac = acetylacetonato; L1 = 1,3-bis-(2,6-diisopropylphenyl)imidazolinylidene and L2 = 1,3-bis-(2,4,6-trimethylphenyl)imidazolinylidene) complexes were prepared by the action of the parent carbene on [Rh(acac)(CO)2] in THF. The crystal structure characterisation of [Rh(acac)(CO)(L1)] revealed a slightly distorted square planar geometry with the carbene ligand orientated almost perpendicular to the equatorial plane; an elongated trans Rh-O bond of 2.0806(18) ? reflecting the considerable trans-influence of the carbene ligand. By measuring the CO stretching frequencies in a range of [Rh(acac)(CO)(L)] complexes (L = CO, L1, L2, PPh 3, PnBu3, P(O-2,4-tBu 2-Ph)3) the following electron donating ability series was established: L1 ～ L2 ～ PnBu 3 > PPh3 > P(O-2,4-tBu 2-Ph)3 > CO; indicating the carbenes investigated in this study to have a similar electronic cis-influence as trialkyl phosphines. Both complexes do not display hydroformylation activity towards 1-hexene in the absence of added phosphine or phosphite ligands under the conditions investigated (P = 60; T = 85 °C). In the presence of a phosphine or phosphite ligand the resulting hydroformylation catalysis was identical to that observed for [Rh(acac)(CO)2] and the corresponding ligand and subsequent high-pressure 31P NMR studies confirmed substitution of the carbene ligand under these conditions.

Hydroformylation of oct-1-ene catalyzed by dinuclear gem-dithiolato-bridged rhodium(I) complexes and phosphorus donor ligands

The dinuclear gem-dithiolato bridged compounds [Rh2(μ-S2Cptn)(cod)2] (1) (CptnS22- = 1,1-cyclopentanedithiolato), [Rh2(μ-S2Chxn)(cod)2] (2) (ChxnS22-/

Supraphos: A supramolecular strategy to prepare bidentate ligands

Herein, we report a new strategy for the preparation of chelating bidentate ligands, which involves the mixing of two mondentate ligands functionalized with complementary binding sites. The assembly process is based on selective metal-ligand interactions

Dormant states of rhodium hydroformylation catalysts: Carboalkoxyrhodium complex formed from enones in the alkene feed

Catalysts get food poisoning: Conversion of the active 1-alkene hydroformylation catalyst 1 with reactive impurities in the feed, such as dienes and enones, into unreactive rhodium intermediates leads to deactivation of 1. For example, 2 is much more reac

High-pressure infrared studies of rhodium complexes containing thiolate bridge ligands under hydroformylation conditions

In situ high-pressure IR spectroscopy studies of the rhodium catalyst systems [Rh2{μ-S(CH2)3N(Me2)} 2(COD)2]/PR3 (R = Ph, OPh), [Rh2{μ-S(CH2)2S}(COD)2]/PPh 3, [Rh2{μ-S(CH2)4S}-(COD)2] 2/PPh3, [Rh2{μ-XANTOSS}(COD)2]2/PPh3, and [Rh(acac)(CO)2]/PR3 (R = Ph, OPh) revealed the presence of mononuclear rhodium hydride species under hydroformylation conditions (80°C, 5-30 bar). The activities and selectivities, obtained during the hydroformylation of 1-hexene using these systems as catalyst precursors, can be fully accounted for by the mononuclear species observed. Deuterioformylation experiments using dinuclear [Rh2{μ-S(CH2)3N(Me2)} 2(COD)2]/PR3 systems lent no support to a dinuclear mechanism.

Rhodium hydride (HRh(CO)(PPh3)3) and rhodium carbonyl (Rh4(CO)8L4) complexes obtained by reaction of Rh(acac)(CO)(L) type complexes with methanol and formaldehyde

Rhodium(I) complexes of Rh(acac)(CO)(L) type (where L = P(OMe)3, P(OEt)3, P(OPh)3, P(O-o-MeC6H4)3, PPh3, P(p-MeC6H4)3, PMePh2, AsPh3) react with alcohols and formaldehyde.In absence of free ligand (L) only carbonyl complexes of formula Rh4(CO)8(L)4 (or Rh

MECHANISM OF PHOSPHINE-MODIFIED RHODIUM-CATALYZED HYDROFORMYLATION STUDIED BY CIR-FTIR.

The mechanism of phosphine-modified rhodium-catalyzed hydroformylation of 1-hexene was studied by in situ infrared spectroscopy using high pressure autoclaves equipped with embedded cylindrical internal reflectance crystals (CIR-FTIR). A series of RhH(CO)//2(PR//3)//2 complexes were synthesized using p-substituted triarylphosphines where the electron density on rhodium was varied by using p-N(CH//3)//2, p-OCH//3, p-H, p-F, p-Cl or p-CF//3. The metal carbonyl and metal hydride infrared stretching frequencies were correlated by a standard Hammett treatment of the data. Reaction rates and selectivities for linear aldehydes both increased with increasingly electron-withdrawing phosphines. The rate and spectroscopic data permitted the assignment of a reaction mechanism involving CO dissociation from RhH(CO)//2L//2 as the primary selective hydroformylation pathway.