N-Heterocyclic carbene–rhodium complexes as catalysts for hydroformylation and related reactions

Gil, Wojciech; Trzeciak, Anna M.

doi:10.1016/j.ccr.2010.11.005

Cited by 102 publications

(41 citation statements)

References 64 publications

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“…[14][15][16] There are only a few examples where such polymer metal complexes act as catalysts, which include epoxidation, hydrosilylation, hydroformylation, and hydrolysis. [17][18][19][20] A vast number of N-heterocyclic organometallic compounds have been applied toward the polymerization of ethylene owing to their low cost, low toxicity, and abundance, rendering them versatile precursors. …”

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confidence: 99%

Synthesis and Characterization of Polymer Metal Complexes and Their Catalytic Activity in Ethylene Oligomerization

Ahamad

Alshehri

2013

Adv Polym Technol

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ABSTRACT:A new polymeric ligand, 4,7-dihydroxy-1,10-phenanthroline/formaldehyde polymeric ligand [poly-(DHPF)], was synthesized via the polycondensation of 4,7-dihydroxy-1,10-phenanthroline and formaldehyde in an acidic medium. Polymer metal complexes, poly-[DHPF-M(II)Cl 2 ], were subsequently prepared with Co(II) and Ni(II) ions. The synthesized polymers were characterized by elemental and spectral analyses. The polymer metal complexes were evaluated as catalyst precursors for ethylene oligomerization, using methylaluminoxane as an activator. Different Al/M [M = Co(II) and Ni(II)] ratios were investigated at two different ethylene pressures. Poly-[DHPF-Co(II)Cl 2 ] (C 1 ) and poly-([DHPF-Ni(II)Cl 2 ] (C 2 ) were isolated as blue and green solids, respectively. Complex C 2 was found to be a more effective precatalyst than C 1 in the presence of a cocatalyst. Thus, C 2 exhibited the maximum activity of 1.92 × 10 6 g mol −1 (Ni) h −1 bar −1 with an Al/Ni ratio of 3000:1 at room temperature, whereas C 1 exhibited a maximum activity of 1.87 × 10 6 g mol −1 (Co) h −1 bar −1 with a 5-atm pressure of ethylene. Upon increasing the Al/Co ratio at 1 atm pressure of ethylene, the catalytic activity of precatalyst increased and the process became more selective for higher oligomers. The catalytic activity and selectivity with 1-decene using C 1 were 3.16 × 10 5 g mol −1 (Co) h −1 bar −1 and 72%, respectively, with 5 atm ethylene and an Al/Co ratio of 300:1. C

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confidence: 99%

Synthesis and Characterization of Polymer Metal Complexes and Their Catalytic Activity in Ethylene Oligomerization

Ahamad

Alshehri

2013

Adv Polym Technol

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“…for C-C coupling, 5 olefin metathesis 6 and hydroformylation. 7 Recently, so-called abnormal or mesoionic carbenes 8 have been investigated as a subclass of NHC ligands which bind the metal through the imidazole C4 or C5 site. 9 These abnormal 35 carbenes have demonstrated stronger σ-donor properties than their C2-bound congeners, thus facilitating the oxidative addition to the bound metal center.…”

Section: Introductionmentioning

confidence: 99%

Platinum(ii) and platinum(iv) complexes stabilized by abnormal/mesoionic C4-bound dicarbenes

et al. 2013

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“…1.7). Apparently, the carbene was active in both ways, as catalyst in the acyloin reaction and as ligand in the hydroformylation reaction 27. This was supported by the different yields for the aldehyde 2 with 58 % if applying C1 (no.…”

Section: Resultsmentioning

confidence: 92%

“…Only 2 % of isomer 4 were obtained. Under comparable conditions we applied imidazolium salts as carbene precursors as well (Figure 2), because Rh/imidazole NHCs are well known for their activity in the hydroformylation 27. 28 These imidazole NHCs displayed comparable high yields up to 92 % for 2 in the hydroformylation step.…”

Section: Resultsmentioning

confidence: 99%

Decreasing Side Products and Increasing Selectivity in the Tandem Hydroformylation/Acyloin Reaction

et al. 2015

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A highly selective catalyst system was developed for the recently discovered tandem hydroformylation/acyloin reaction by systematic investigations and changes of reaction conditions. This new catalyst system is characterized by an excellent selectivity of the desired reaction pathway with negligible amounts of side products. A successful application of the tandem hydroformylation/acyloin reaction to a variety of olefins is enabled with comparable excellent selectivities up to >99 % for the first and second reaction step, therefore a general synthesis for the conversion of olefins into acyloins is found. Furthermore, very good to excellent yields for the intermediates and final acyloin products were observed within two catalysed reactions in one preparative step. The acyloin product was applied as a nonpolar precursor for surfactants. After attaching a polar head group to the acyloin and determination of tensiometric data, the molecule showed industrial relevant surface‐active properties.

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N-Heterocyclic carbene–rhodium complexes as catalysts for hydroformylation and related reactions

Cited by 102 publications

References 64 publications

Synthesis and Characterization of Polymer Metal Complexes and Their Catalytic Activity in Ethylene Oligomerization

Synthesis and Characterization of Polymer Metal Complexes and Their Catalytic Activity in Ethylene Oligomerization

Platinum(ii) and platinum(iv) complexes stabilized by abnormal/mesoionic C4-bound dicarbenes

Decreasing Side Products and Increasing Selectivity in the Tandem Hydroformylation/Acyloin Reaction

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