Rhodium phosphino-enolate complexes as chemo- and regioselective catalysts for the hydroformylation of styrenes

Uh, Yoon-Seo; Boyd, Alaina R.; Little, Vanessa Renee; Jessop, Philip G.; Hesp, Kevin D.; Cipot-Wechsler, Judy; Stradiotto, Mark; McDonald, Robert

doi:10.1016/j.jorganchem.2010.04.032

Cited by 7 publications

(5 citation statements)

References 24 publications

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“…The M-L bond distances for both Rh and Ir complexes are similar as was expected because of their similar covalent radii as deduced from a study of crystallographic data . Comparisons to similar Rh and Ir P–O complexes also show comparable data.…”

Section: Resultssupporting

confidence: 78%

“…Stradiotto and co-workers have reported both neutral and zwitterionic Ir(COD)(P–N) and neutral Ir(COD)(P–O) complexes that are active for olefin hydrogenation. These types of catalysts have also been shown to be active for olefin hydroamination and hydroformylation . Although highly active and enantioselective catalysts already exist, investigations into neutral analogues may prove useful.…”

Section: Resultsmentioning

confidence: 99%

“…These types of catalysts have also been shown to be active for olefin hydroamination 15 and hydroformylation. 16 Although highly active and enantioselective catalysts already exist, investigations into neutral analogues may prove useful. Neutral catalysts are often more soluble in hydrocarbon solvents than in higher dielectric chlorinated solvents and thereby allow greener reaction conditions, as well as avoid the deactivating properties of coordinating solvents.…”

Section: Synthesis Of the Neutral Ni(ii) Complex 2a Containingmentioning

confidence: 99%

“…As a result the prevalence of chelating phosphine and oxygen/nitrogen ligands in late transition metal catalysts, methods for their facile synthesis are valuable and sought-after. Transition metal complexes containing P–O and P–N ligands can catalyze a variety of reactions, including transfer − and direct hydrogenation, − olefin polymerization, , Michael addition, hydroamination, hydroformylation among others. − Specific examples include Ni(II) catalysts containing P–O chelating ligands, which are used in the Shell Higher Olefin Process, where the first step is catalytic oligomerization of ethylene. Olefin hydrogenation catalysts based on Crabtree’s catalyst often contain a P–N , or P–O , ligand.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of New Late Transition Metal P,P-, P,N-, and P,O- Complexes Using Phosphonium Dimers as Convenient Ligand Precursors

et al. 2013

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Always cite the published version, so the author(s) will receive recognition through services that track citation counts, e.g. Scopus. If you need to cite the page number of the author manuscript from TSpace because you cannot access the published version, then cite the TSpace version in addition to the published version using the permanent URI (handle) found on the record page. ABSTRACTThe phosphonium dimer [-Cy2PCH(OH)CH2-]2(X)2, X = Cl -, Brwas used to synthesize and characterize a variety of late transition metal complexes containing chelating phosphino-enolate (PCy2CH=CHO -), imine (PCy2CH2CH=NR, R = Ph, (S)-CHMePh), and oxime (PCy2CH2CH=NOH) ligands. The phosphonium dimer, when deprotected with base, generates the phosphine aldehyde PCy2CH2CHO in situ, which, in the presence of [M(COD)Cl]2, M = Rh, Ir, and a PF6salt, or [Ni(H2O)6][BF4]2, facilitates a condensation reaction with an amine or hydroxylamine to form phosphino-imine or phosphino-oxime metal complexes [M(COD)(P-N)][PF6] or [Ni(P-N)2][X]2, X = ClO4 -, BF4 -, respectively. In the absence of an amine, phosphino-enolate containing complexes are formed. A neutral Ni(II) complex Ni(PCy2CH=CHO)2 with trans-bis(phosphino-enolate) ligands which resemble ligands used on nickel for olefin oligomerization, as well as neutral Rh(I) and Ir(I) 1,5-cyclooctadiene complexes M(COD)(PCy2CH=CHO) are characterized. Both the rhodium and iridium complexes are active olefin hydrogenation catalysts. Reaction of the phosphino-aldehyde with Pt(COD)Cl2 results in the formation of trans-PtCl2(PCy2CH2CHO)2 with pendant aldehyde groups and under certain conditions, they undergo an intraligand aldol condensation to form a diphosphine ligand.

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Section: Resultssupporting

confidence: 78%

Section: Resultsmentioning

confidence: 99%

Section: Synthesis Of the Neutral Ni(ii) Complex 2a Containingmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis of New Late Transition Metal P,P-, P,N-, and P,O- Complexes Using Phosphonium Dimers as Convenient Ligand Precursors

et al. 2013

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“…1,2 The most efficient catalysts reported for this reaction are rhodium complexes, and a large amount of work has been devoted to the improvement of reaction rates and selectivity by ligand design. 3,4 For example, monodentate and bidentate phosphorous-based ligands, [5][6][7][8][9][10][11] N-heterocyclic carbene (NHC), [12][13][14] and the hybrid P,O-or P,N-ligands with multiple ligations to the rhodium center, [15][16][17][18][19][20] have been synthesized by nely tuning their electronic and steric properties to spur the activity and selectivity of the rhodium complexes.…”

Section: Introductionmentioning

confidence: 99%

Immobilization of a rhodium catalyst using a diphosphine-functionalized ionic liquid in RTIL for the efficient and recyclable biphasic hydroformylation of 1-octene

Liu

Wang

et al. 2016

Faraday Discuss.

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A highly efficient and stable Rh-P catalytic system in the RTIL of [PEmim]BF4 was developed for the biphasic hydroformylation of 1-octene by using the diphosphine-functionalized ionic liquid (FIL) of 2. While 2-Rh(acac)(CO)2 was immobilized in [PEmim]BF4 (solvent), a typical biphasic catalysis was fulfilled with advantages of facile separation and recycling ability - 9 runs without any loss of activity. It was found that not only the acquired π-acceptor character of 2, but also the synergetic role of the piperidyl group in [PEmim]BF4 as an N-containing donor, cooperatively contributed to the efficient hydroformylation due to the facilitated formation and stability of the Rh-H active species (ν 2045 cm(-1)). This was supported by the in situ high-pressure FT-IR spectral analysis.

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Metals in Hydroformylation

2016

Hydroformylation

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Rhodium phosphino-enolate complexes as chemo- and regioselective catalysts for the hydroformylation of styrenes

Cited by 7 publications

References 24 publications

Synthesis of New Late Transition Metal P,P-, P,N-, and P,O- Complexes Using Phosphonium Dimers as Convenient Ligand Precursors

Synthesis of New Late Transition Metal P,P-, P,N-, and P,O- Complexes Using Phosphonium Dimers as Convenient Ligand Precursors

Immobilization of a rhodium catalyst using a diphosphine-functionalized ionic liquid in RTIL for the efficient and recyclable biphasic hydroformylation of 1-octene

Metals in Hydroformylation

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