N-Acetyl-N,N-dipyrid-2-yl (cyclooctadiene) rhodium (I) and iridium (I) complexes: Synthesis, X-ray structures, their use in hydroformylation and carbonyl hydrosilylation reactions and in the polymerization of diazocompounds

Bantu, Bhasker; Wurst, Klaus; Buchmeiser, Michael R.

doi:10.1016/j.jorganchem.2007.08.009

Cited by 20 publications

(22 citation statements)

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“…The synthesis of norborn-5-ene-( N,N -dipyrid-2-yl)carbamide ( M1 ) was accomplished via reaction of norborn-5-ene-2-ylcarboxylic acid chloride with dipyrid-2-ylamine in the presence of triethylamine as described elsewhere [ 9 ]. exo,exo -[2-(3-Ethoxycarbonyl-7-oxabicyclo[2.2.1]hept-5-ene-2-carbonyloxy)ethyl]trimethylammonium iodide ( M2 ) was prepared in a four-step procedure ( Scheme 1 ).…”

Section: Resultsmentioning

confidence: 99%

“…Next, poly( M1 - b - M2 ) was loaded with Rh(I) via reaction of poly( M1 - b - M2 ) with [RhCl(COD)] 2 (COD = cycloocta-1,5-diene) to yield poly( M1 - b - M2 ) -Rh ( Scheme 2 ). A metal loading of 18 mg Rh/g polymer was achieved, which corresponds to 12% of the theoretical loading (assuming the formation of a mono-dipyridyl-Rh(I) complex as observed for M1 ) [ 9 ]. Consequently, almost 90% of the dipyrid-2-ylamide ligands were not involved in complex formation, which is of importance for the catalytic behavior of the supported catalyst and for metal leaching.…”

Section: Resultsmentioning

confidence: 99%

“…Here, we used poly( M1 - b - M2 ) -Rh for the hydroformylation of 1-octene in water. For purposes of comparison, the results obtained were compared to those previously obtained with the homogeneous analogue CH 3 CON(Py) 2 RhCl(COD) ( C1 ) [ 9 ].…”

Section: Resultsmentioning

confidence: 99%

“…GC-MS investigations were carried out on a Shimadzu GCMS-QP5050 with an AOC-20i Autosampler using a SPB fused silica (Rxi-5MS) column (30 m × 0.25 mm × 0.25 μm film thickness, 60.6 kPa, temperature program: 70 °C – 300 °C, 25 min). The Schrock initiator Mo( N -2,6-Me 2 -C 6 H 3 )[CHC(CH 3 ) 2 Ph][OCMe(CF 3 ) 2 ] 2 [Mo] [22], N,N- dipyridyl- endo -norborn-5-ene-2-carbamide ( M1 ) [9,37] and N -acetyl- N,N -dipyrid-2-yl (cyclooctadiene) rhodium chloride ( C1 ) [9] were synthesized according to the literature.…”

Section: Methodsmentioning

confidence: 99%

“…This leads to high educt concentrations at the polymer-bound catalyst, often resulting in high reaction rates in water [ 8 ]. We recently reported on the synthesis of Rh I and Ir I complexes of N,N -dipyrid-2-ylacetamide and their use in hydroformylation reactions [ 9 ]. Here, we report on the immobilization of a Rh- N,N -dipyrid-2-ylacetamide-based catalyst on a soluble, amphiphilic, ring-opening metathesis polymerization- (ROMP) derived block copolymer and its use in hydroformylation [ 10 ] under micellar conditions [ 3 , 5 , 11 ].…”

Section: Introductionmentioning

confidence: 99%

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Ring opening metathesis polymerization-derived block copolymers bearing chelating ligands: synthesis, metal immobilization and use in hydroformylation under micellar conditions

Pawar

Weckesser²,

Blechert³

et al. 2010

Beilstein J. Org. Chem.

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SummaryNorborn-5-ene-(N,N-dipyrid-2-yl)carbamide (M1) was copolymerized with exo,exo-[2-(3-ethoxycarbonyl-7-oxabicyclo[2.2.1]hept-5-en-2-carbonyloxy)ethyl]trimethylammonium iodide (M2) using the Schrock catalyst Mo(N-2,6-Me2-C6H3)(CHCMe2Ph)(OCMe(CF3)2)2 [Mo] to yield poly(M1-b-M2). In water, poly(M1-b-M2) forms micelles with a critical micelle-forming concentration (cmc) of 2.8 × 10−6 mol L−1; Reaction of poly(M1-b-M2) with [Rh(COD)Cl]2 (COD = cycloocta-1,5-diene) yields the Rh(I)-loaded block copolymer poly(M1-b-M2)-Rh containing 18 mg of Rh(I)/g of block copolymer with a cmc of 2.2 × 10−6 mol L−1. The Rh-loaded polymer was used for the hydroformylation of 1-octene under micellar conditions. The data obtained were compared to those obtained with a monomeric analogue, i.e. CH3CON(Py)2RhCl(COD) (C1, Py = 2-pyridyl). Using the polymer-supported catalyst under micellar conditions, a significant increase in selectivity, i.e. an increase in the n:iso ratio was accomplished, which could be further enhanced by the addition of excess ligand, e.g., triphenylphosphite. Special features of the micellar catalytic set up are discussed.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Ring opening metathesis polymerization-derived block copolymers bearing chelating ligands: synthesis, metal immobilization and use in hydroformylation under micellar conditions

Pawar

Weckesser²,

Blechert³

et al. 2010

Beilstein J. Org. Chem.

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Hydrogen: a good partner for rhodium‐catalyzed hydrosilylation

Balan

Pop

Comte

et al. 2014

Applied Organom Chemis

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The influence of hydrogen pressure on the hydrosilylation of ketones catalyzed by [((S)-SYNPHOS)Rh(nbd)]OTf has been studied. We have notably demonstrated that hydrogen significantly affected the outcome of the reaction while not being consumed as stoichiometric reducing agent. In THF, diethyl ether or toluene, the hydrogen pressure exceedingly accelerated the hydrosilylation reaction and preserved or even improved the enantioselectivity of the process. In CH 2 Cl 2 , the rhodium catalyst also showed generally higher catalytic activity under hydrogen pressure. Most serendipitously, several ketones were found to give products of absolute opposite configuration upon performing the hydrosilylation under argon atmosphere or under hydrogen pressure.

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On the “Tertiary Structure” of Poly‐Carbenes; Self‐Assembly of sp³‐Carbon‐Based Polymers into Liquid‐Crystalline Aggregates

Franssen

Ensing

Hegde

et al. 2013

Chemistry A European J

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The self-assembly of poly(ethylidene acetate) (st-PEA) into van der Waals-stabilized liquid-crystalline (LC) aggregates is reported. The LC behavior of these materials is unexpected, and unusual for flexible sp(3)-carbon backbone polymers. Although the dense packing of polar ester functionalities along the carbon backbone of st-PEA could perhaps be expected to lead directly to rigid-rod behavior, molecular modeling reveals that individual st-PEA chains are actually highly flexible and should not reveal rigid-rod induced LC behavior. Nonetheless, st-PEA clearly reveals LC behavior, both in solution and in the melt over a broad elevated temperature range. A combined set of experimental measurements, supported by MM/MD studies, suggests that the observed LC behavior is due to self-aggregation of st-PEA into higher-order aggregates. According to MM/MD modeling st-PEA single helices adopt a flexible helical structure with a preferred trans-gauche syn-syn-anti-anti orientation. Unexpectedly, similar modeling experiments suggest that three of these helices can self-assemble into triple-helical aggregates. Higher-order assemblies were not observed in the MM/MD simulations, suggesting that the triple helix is the most stable aggregate configuration. DLS data confirmed the aggregation of st-PEA into higher-order structures, and suggest the formation of rod-like particles. The dimensions derived from these light-scattering experiments correspond with st-PEA triple-helix formation. Langmuir-Blodgett surface pressure-area isotherms also point to the formation of rod-like st-PEA aggregates with similar dimensions as st-PEA triple helixes. Upon increasing the st-PEA concentration, the viscosity of the polymer solution increases strongly, and at concentrations above 20 wt % st-PEA forms an organogel. STM on this gel reveals the formation of helical aggregates on the graphite surface-solution interface with shapes and dimensions matching st-PEA triple helices, in good agreement with the structures proposed by molecular modeling. X-ray diffraction, WAXS, SAXS and solid state NMR spectroscopy studies suggest that st-PEA triple helices are also present in the solid state, up to temperatures well above the melting point of st-PEA. Formation of higher-order aggregates explains the observed LC behavior of st-PEA, emphasizing the importance of the "tertiary structure" of synthetic polymers on their material properties.

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N-Acetyl-N,N-dipyrid-2-yl (cyclooctadiene) rhodium (I) and iridium (I) complexes: Synthesis, X-ray structures, their use in hydroformylation and carbonyl hydrosilylation reactions and in the polymerization of diazocompounds

Cited by 20 publications

References 53 publications

Ring opening metathesis polymerization-derived block copolymers bearing chelating ligands: synthesis, metal immobilization and use in hydroformylation under micellar conditions

Ring opening metathesis polymerization-derived block copolymers bearing chelating ligands: synthesis, metal immobilization and use in hydroformylation under micellar conditions

Hydrogen: a good partner for rhodium‐catalyzed hydrosilylation

On the “Tertiary Structure” of Poly‐Carbenes; Self‐Assembly of sp³‐Carbon‐Based Polymers into Liquid‐Crystalline Aggregates

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N-Acetyl-N,N-dipyrid-2-yl (cyclooctadiene) rhodium (I) and iridium (I) complexes: Synthesis, X-ray structures, their use in hydroformylation and carbonyl hydrosilylation reactions and in the polymerization of diazocompounds

Cited by 20 publications

References 53 publications

Ring opening metathesis polymerization-derived block copolymers bearing chelating ligands: synthesis, metal immobilization and use in hydroformylation under micellar conditions

Ring opening metathesis polymerization-derived block copolymers bearing chelating ligands: synthesis, metal immobilization and use in hydroformylation under micellar conditions

Hydrogen: a good partner for rhodium‐catalyzed hydrosilylation

On the “Tertiary Structure” of Poly‐Carbenes; Self‐Assembly of sp3‐Carbon‐Based Polymers into Liquid‐Crystalline Aggregates

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On the “Tertiary Structure” of Poly‐Carbenes; Self‐Assembly of sp³‐Carbon‐Based Polymers into Liquid‐Crystalline Aggregates