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Reaction of bis(dicyclohexylphosphino)ethane dioxide with hydrogen peroxide leads to an extended crystalline network based on the formation of hydrogen bonds with the PO groups of the diphosphine dioxide. The structural motif of the network is characterized by X-ray diffraction. A new selective synthesis for an industrially important MEKPO (methyl ethyl ketone peroxide) dimer is described. The dimer is created by reaction of dppe dioxide (bis(diphenylphosphino)ethane dioxide) with butanone and hydrogen peroxide. This peroxide is stabilized by forming strong hydrogen bonds to the phosphine oxide groups within an extended network, which has been characterized by single crystal X-ray diffraction. Reaction of acetylacetone with hydrogen peroxide, irrespective of the presence of phosphine oxide, leads to the stereoselective formation of two dioxolanes. Both cyclic peroxides have been obtained in crystalline forms suitable for single crystal X-ray diffractions.
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Phosphine‐Ligated Cobalt(II) Acetylacetonate Complexes
Cobalt(II) acetylacetonate complexes bearing a phosphine ligand can be key intermediates or precursors to cobalt‐based catalysts; however, they have been rarely studied, especially from a molecular structure point of view. This work is focused on the understanding of how different phosphines react with Co(acac)2(acac = acetylacetonate). To do so, a variety of analytical tools, including NMR and IR spectroscopy, X‐ray crystallography, mass spectrometry, and elemental analysis, have been used to study the reactions and characterize the isolated products. These results have shown that the monodentate ligand, HPPh2, binds to Co(acac)2weakly and reversibly to produce Co2(acac)4(HPPh2), whereas the bidentate ligand, 1,2‐bis(diphenylphosphino)ethane (dppe), interacts with Co(acac)2more strongly to yield a 1D coordination polymer of Co(acac)2(dppe). 2‐(Dicyclohexylphosphino)methyl‐1 H‐pyrrole (CyPNH), which is a pyrrole‐tethered phosphine, forms an unusual 5‐coordinate cobalt complex, Co(acac)2(CyPNH), in which the pyrrole moiety participates in a bifurcated hydrogen–bonding interaction with the [acac]–ligands. In contrast, another bidentate ligand, 4,5‐bis(diphenylphosphino)‐9,9‐dimethylxanthene (xantphos), fails to react with Co(acac)2, presumably due to its wide bite angle and difficulty in bridging two metals.
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- PAR ID:
- 10631847
- Publisher / Repository:
- Wiley-VCH GmbH
- Date Published:
- Journal Name:
- European Journal of Inorganic Chemistry
- Volume:
- 28
- Issue:
- 19
- ISSN:
- 1434-1948
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript
- Journal Article:
- https://doi.org/10.1002/ejic.202500157
