Dataset Information

Solubility of Iridium and Ruthenium Organometallic Photoredox Catalysts.

ABSTRACT: Despite the exponential growth of the field of photocatalysis, for reasons that are not entirely clear, these precious photocatalysts are often used in the literature at loadings that exceed their maximum solubility. On an industrial scale, the quantity of any precious metal catalyst can be a substantial financial burden or a sourcing issue, not to mention concerns as to the ecological and earth abundance of these catalysts. We believe that inattention to solubility has made these reactions appear less efficient than they actually are, because much of the photocatalyst remains undissolved. Therefore, the maximum solubilities of iridium and ruthenium centered photocatalysts have been systematically identified in industrially relevant solvents. Further, a literature photocatalytic reaction which our results suggested was beyond the maximum solubility has been revisited, with interesting results.

SUBMITTER: Jespersen D

PROVIDER: S-EPMC6687329 | biostudies-literature | 2019 May

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Solubility of Iridium and Ruthenium Organometallic Photoredox Catalysts.

Jespersen Daniel D Keen Brockton B Day Jon I JI Singh Anuradha A Briles Justin J Mullins Duncan D Weaver Jimmie D JD

Organic process research & development 20190318 5

Despite the exponential growth of the field of photocatalysis, for reasons that are not entirely clear, these precious photocatalysts are often used in the literature at loadings that exceed their maximum solubility. On an industrial scale, the quantity of any precious metal catalyst can be a substantial financial burden or a sourcing issue, not to mention concerns as to the ecological and earth abundance of these catalysts. We believe that inattention to solubility has made these reactions appe ...[more]

PMID: 31396008

Similar Datasets

Project description:A ruthenium aqua photoredox catalyst has been successfully heterogeneneized on graphene oxide (GO@trans-fac-3) and graphite rods (GR@trans-fac-3) for the first time and have proven to be sustainable and easily reusable systems for the photooxidation of alcohols in water, in mild and green conditions. We report here the synthesis and total characterization of two Ru(II)-polypyridyl complexes, the chlorido trans-fac-[RuCl(bpea-pyrene)(bpy)](PF6) (trans-fac-2) and the aqua trans-fac-[Ru(bpea-pyrene)(bpy)OH2](PF6)2 (trans-fac-3), both containing the N-tridentate, 1-[bis(pyridine-2-ylmethyl)amino]methylpyrene (bpea-pyrene), and 2,2'-bipyridine (bpy) ligands. In both complexes, only a single isomer, the trans-fac, has been detected in solution and in the solid state. The aqua complex trans-fac-3 displays bielectronic redox processes in water, assigned to the Ru(IV/II) couple. The trans-fac-3 complex has been heterogenized on different types of supports, (i) on graphene oxide (GO) through π-stacking interactions between the pyrene group of the bpea-pyrene ligand and the GO and (ii) both on glassy carbon electrodes (GC) and on graphite rods (GR) through oxidative electropolymerization of the pyrene group, which yield stable heterogeneous photoredox catalysts. GO@trans-fac-3- and GR/poly trans-fac-3-modified electrodes were fully characterized by spectroscopic and electrochemical methods. Trans-fac-3 and GO@trans-fac-3 photocatalysts (without a photosensitizer) showed good catalytic efficiency in the photooxidation of alcohols in water under mild conditions and using visible light. Both photocatalysts display high selectivity values (>99%) even for primary alcohols in accordance with the presence of two-electron transfer processes (2e-/2H+). GO@trans-fac-3 keeps intact its homogeneous catalytic properties but shows an enhancement in yields. GO@trans-fac-3 can be easily recycled by filtration and reused for up to five runs without any significant loss of catalytic activity. Graphite rods (GR@trans-fac-3) were also evaluated as heterogeneous photoredox catalysts showing high turnover numbers (TON) and selectivity values.

Dataset Information

Solubility of Iridium and Ruthenium Organometallic Photoredox Catalysts.

Publications

Solubility of Iridium and Ruthenium Organometallic Photoredox Catalysts.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets