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A Cp^tt-Based Trioxo-Rhenium Catalyst for the Deoxydehydration of Diols and Polyols.

ABSTRACT: Trioxo-rhenium complexes are well known catalysts for the deoxydehydration (DODH) of vicinal diols (glycols). In this work, we report on the DODH of diols and biomass-derived polyols using Cp^ttReO₃ as a new catalyst (Cp^tt=1,3-di-tert-butylcyclopentadienyl). The DODH reaction was optimized using 2?mol?% of Cp^ttReO₃ and 3-octanol as both reductant and solvent. The Cp^ttReO₃ catalyst exhibits an excellent activity for biomass-derived polyols. Specifically, glycerol is almost quantitatively converted to allyl alcohol and mucic acid gives 75?% of muconates at 91?% conversion. In addition, the loading of Cp^ttReO₃ can be reduced to 0.1?mol?% to achieve a turn-over number as high as 900 per Re when using glycerol as substrate. Examination of DODH reaction profiles by NMR spectroscopy indicates that catalysis is related to Cp-ligand release, which raises questions on the nature of the actual catalyst.

SUBMITTER: Li J

PROVIDER: S-EPMC6472585 | biostudies-literature | 2018 Oct

REPOSITORIES: biostudies-literature

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A Cptt-Based Trioxo-Rhenium Catalyst for the Deoxydehydration of Diols and Polyols.

Li Jing J Lutz Martin M Otte Matthias M Klein Gebbink Robertus J M RJM

ChemCatChem 20180925 20

Trioxo-rhenium complexes are well known catalysts for the deoxydehydration (DODH) of vicinal diols (glycols). In this work, we report on the DODH of diols and biomass-derived polyols using CpttReO3 as a new catalyst (Cptt=1,3-di-tert-butylcyclopentadienyl). The DODH reaction was optimized using 2 mol % of CpttReO3 and 3-octanol as both reductant and solvent. The CpttReO3 catalyst exhibits an excellent activity fo ...[more]

PMID: 31007775

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Project description:Neutral {CpFeII(CO)2[SnII(Pc•3-)]} {Cp is cyclopentadienyl (1, 2) or Cp* is pentamethylcyclopentadienyl (3); Pc: phthalocyanine}, {Cp*FeII(CO)2[SnII(Nc•3-)]} (4, Nc: naphthalocyanine), and {CpFeII(CO)2[SnII(TPP•3-)]} (5, TPP: tetraphenylporphyrin) complexes in which CpFeII(CO)2 fragments (Cp: Cp or Cp*) are coordinated to SnII(macrocycle•3-) have been obtained. The product complexes were obtained at the reaction of charge transfer from CpFeI(CO)2 (Cp: Cp or Cp*) to [SnII(macrocycle2-)] to form the diamagnetic FeII and paramagnetic radical trianionic macrocycles. As a result, these formally neutral complexes contain S = 1/2 spins delocalized over the macrocycles. This provides alternation of the C-Nimine or C-Cmeso bonds in the macrocycles, the appearance of new bands in the near-infrared spectra of the complexes, and blue shift of both Soret and Q-bands. The {CpFeII(CO)2SnII(macrocycle•3-)} units (Cp: Cp or Cp*, macrocycle: Pc or Nc) form closely packed π-stacking dimers in 1 and 3 or one-dimensional chains in 2 and 4 with effective π-π interaction between the macrocycles. Such packing allows strong antiferromagnetic coupling between S = 1/2 spins. Magnetic interaction can be described well by the Heisenberg model for the isolated dimers in 1 and 3 with exchange interaction J/k B = -78 and -85 K, respectively. Magnetic behavior of 2 and 4 is described well by the model that includes contributions from an antiferromagnetically coupled S = 1/2 dimer (J intra) and a Heisenberg S = 1/2 chain with alternating antiferromagnetic spin exchange between the neighbors (J inter). Compound 2 demonstrates large intradimer interaction of J intra/k B = -54 K and essentially weaker interdimer exchange interactions of J inter/k B = -6 K, whereas compound 4 shows strong magnetic coupling of spins within the dimers (J intra/k B = -170 K) as well as between the dimers (J inter/k B = -40 K). Compound {CpFeII(CO)2[SnII(TPP•3-)]} (5) shows no π-π interactions between the porphyrin macrocycles, and magnetic coupling is weak in this case (Weiss temperature is -5 K). Preparation of a similar complex with indium(III) chloride phthalocyanine yields {CpFe(CO)2[In(Pc2-)]} (6). In this complex, indium(III) atoms are reduced instead of the phthalocyanine macrocycles that explains electron paramagnetic resonance silence of 6 in the 4-295 K range.

Dataset Information

A Cp^tt-Based Trioxo-Rhenium Catalyst for the Deoxydehydration of Diols and Polyols.

Publications

A Cp<sup>tt</sup>-Based Trioxo-Rhenium Catalyst for the Deoxydehydration of Diols and Polyols.

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