18346-73-1

Upstream product

• 101-02-0 triphenyl phosphite 
• 25966-20-5 Rh(P(OC₆H₅)3)4⁽¹⁺⁾*ClO₄^(1-) = Rh(P(OC₆H₅)3)4ClO₄ 
• 108-89-4 picoline 
• 24651-65-8 hydridotetrakis(triphenyl phosphite)rhodium(I) 
• 108-99-6 3-Methylpyridine 
• 13269-52-8 trans-3-Hexene 
• 201230-82-2 carbon monoxide 
• 1333-74-0 hydrogen 
• 85100-77-2 1-n-butyl-3-methylimidazolim bromide 
• 592-41-6 1-hexene 

Downstream Products

• 620168-51-6 [Rh(CO)(P(OC₆H₅)3)3]⁽¹⁺⁾*CF₃SO₃^(1-)=[Rh(CO)(P(OC₆H₅)3)3]CF₃SO₃ 
• 620168-50-5 [Rh(CO)(P(OC₆H₅)3)3]⁽¹⁺⁾*BF₄^(1-)=[Rh(CO)(P(OC₆H₅)3)3]BF₄ 

Relevant academic research and scientific papers

Rhodium(I) N-heterocyclic carbene complexes as highly selective catalysts for 1-hexene hydroformylation

Rhodium(I) carbene complexes of the type [Rh(NHC)(cod)X] (where NHC = N-heterocyclic carbene obtained from dialkylimidazolium cation; cod = 1,5-cyclooctadiene; X = Cl, Br, I, SCN) with P(OPh)3 as a modifying ligand have been found to be very active catalysts for 1-hexene hydroformylation under mild conditions (80 °C, 10 atm of H2/CO, 4 h). Even at a low rhodium concentration (1-hexene]/[Rh] = 2000), aldehydes have been obtained in yields of up to 90% with a high n/iso ratio of ca. 7. During the catalytic process, rhodium(1) carbene complexes, [Rh(NHC)(P(OPh)3) 2X], reacted with H2/CO, giving a catalytically active rhodium(I) hydrido complex containing an N-heterocyclic carbene ligand. The presence of [HRh(CO)(P(OPh)3)3] and [Rh(NHC)(P(OPh) 3)(CO)X] complexes in the catalytic system has been confirmed. When P(OCH2CF3)3 was used as modifying ligand with [Rh(NHC)(cod)Br] as catalyst precursor, formation of [HRh(CO)(NHC)(P(OCH 2CF3)3)2] with a square-pyramidal structure was evidenced by 1H and 31P NMR.

New insight into role of ortho-metallation in rhodium triphenylphosphite complexes. Hydrogen mobility in hydrogenation and isomerization of unsaturated substrates

The hydrogen transfer from two rhodium(I) hydrido complexes HRh{P(OPh)3}4 and HRh(CO){P(OPh)3}3 to methyl acrylate and/or allylbenzene leads to the formation of ortho-metallated complexes Rh{P(OC6H4)(OPh)2}{P(OPh)3} 3 (I) and Rh{P(OC6H4)(OPh)2}(CO){P(OPh)3} 2 (II), respectively. During these reactions unsaturated substrates, methyl acrylate or allylbenzene undergo stoichiometric hydrogenation. A similar reaction was also observed for HRh{P(OR)3}4 complexes (R=3-CH3C6H4, 4-CH3C6H4). The complex HRh{P(OPh)3}4 catalyses the isomerization of hex-1-ene to hex-2-ene in the absence of H2; however at 1 atm of H2 the formation of hexane is observed. Hydrido complexes of the type HRh{P(OR)3}4 in D2 atmosphere undergo H/D exchange at the ortho position of coordinated triarylphosphite. Deuteration of the ortho protons in complexes with R=Ph, 3,5-(CH3)2C6H3 and 4-CH3C6H4 is total, whereas only one ortho hydrogen is replaced in the case of R=3-CH3C6H4. The formation of an ortho-metallated chelating ring causes a downfield shift in the 1H-NMR signal of one proton from the phenyl ring to δ ca. 8 ppm.

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.

1,5-Hexadiene selective hydroformylation reaction catalyzed with Rh(acac)2/P(OPh)3 and Rh(acac)(CO)(PPh3)/PPh3 complexes

Hydroformylation of 1,5-hexadiene, catalyzed by the system Rh(acac)2/P(OPh)3 (I), leads to the formation of mono- and dialdehydes, 4-heptenal, 2-Me-3-hexenal and octane-1,8-dial, 2,5-Me2-hexanedial respectively.The yield of dialdehydes increases with temperature and pressure and reaches 100percent at 80 deg C and 10 atm of CO/H2 = 1.The reaction catalyzed by Rh(acac)(CO)(PPh3)/PPh3 (II) system produces, besides dialdehydes, monoaldehydes with a terminal double bond, namely 6-heptenal and 2-Me-5-hexenal.The migration of the double bonds in monoaldehydes dependsmainly on the donor properties of modifying ligands.Phosphine when used as a modifying ligand (II), because of its strong donor properties, restricts isomerization (double bond migration) and diminishes yield of 4-heptenal.In contrast, when less strongly donating ligands such as phosphite are used as modifying ligands (I), independently of its steric properties, 4-heptenal is the main reaction product.Key words: Hydroformylation; Rhodium; Hexadiene; Catalysis

Hex-1-ene hydroformylation catalyzed by Rh(acac)2 modified with amines, formation of reactive HRh(CO)3 und unreactive Rh4(CO)84 species

Pyridines and amines have been used as modifying ligands in the hex-1-ene hydroformylation reaction catalyzed by Rh(acac)2.Aldehydes (n + iso) were obtained in 80-85 percent yield.The active form of the catalyst has been isolated as the solid HRh(CO)3.Another complex formed in the reaction of Rh(acac)2 with H2 and CO in the presence of pyridine, Rh4(CO)84, is catalytically inactive.