Hydrogen-Bonded Di(hydroperoxy)alkane Adducts of the Type Cy<sub>3</sub>P=O·(HOO)<sub>2</sub>CHR (R = Alkyl)

Hydrogen-Bonded Di(hydroperoxy)alkane Adducts of the Type Cy<sub>3</sub>P=O·(HOO)<sub>2</sub>CHR (R = Alkyl)

Five representatives of a novel type of di(hydroperoxy)alkane adducts of phosphine oxides have been synthesized and fully characterized, including their solubility in organic solvents. The phosphine oxide Cy<sub>3</sub>PO (<b>1</b>) has been used in combination with the corre...

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Bibliographic Details
Main Authors: Rahym Ashirov, Maya Todorovic, Nattamai Bhuvanesh, Janet Blümel
Format: Article
Language:English
Published: MDPI AG 2025-01-01
Series:Molecules
Subjects:
phosphine oxides
di(hydroperoxy)alkanes
X-ray structures
multinuclear NMR
IR data
Online Access:https://www.mdpi.com/1420-3049/30/2/329
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Summary:Five representatives of a novel type of di(hydroperoxy)alkane adducts of phosphine oxides have been synthesized and fully characterized, including their solubility in organic solvents. The phosphine oxide Cy<sub>3</sub>PO (<b>1</b>) has been used in combination with the corresponding aldehydes to create the adducts Cy<sub>3</sub>PO·(HOO)<sub>2</sub>CHCH<sub>3</sub> (<b>2</b>), Cy<sub>3</sub>PO·(HOO)<sub>2</sub>CHCH<sub>2</sub>CH<sub>3</sub> (<b>3</b>), Cy<sub>3</sub>PO·(HOO)<sub>2</sub>CH(CH<sub>2</sub>)<sub>2</sub>CH<sub>3</sub> (<b>4</b>), Cy<sub>3</sub>PO·(HOO)<sub>2</sub>CH(CH<sub>2</sub>)<sub>3</sub>CH<sub>3</sub> (<b>5</b>), and Cy<sub>3</sub>PO·(HOO)<sub>2</sub>CH(CH<sub>2</sub>)<sub>7</sub>CH<sub>3</sub> (<b>6</b>). All adducts crystallize easily and contain the peroxide and phosphine oxide hydrogen-bonded in 1:1 ratios. The single crystal X-ray structures of <b>2</b>–<b>6</b> and their unique features are discussed. The <sup>31</sup>P NMR spectra of the adducts <b>2</b>–<b>6</b> show downfield-shifted signals as compared to Cy<sub>3</sub>PO. In the IR spectra, the ν(P=O) wavenumbers of the adducts have smaller values than the neat phosphine oxide. All spectroscopic results of <b>2</b>–<b>6</b> show that the P=O bond is weakened by hydrogen-bonding to the di(hydroperoxy)alkane moieties. Adduct <b>6</b> selectively oxidizes PPh<sub>3</sub> to OPPh<sub>3</sub> within minutes, and nonanal is reformed in the process. The easy synthesis, handling, and administration of these stable, solid, and soluble peroxides with well-defined composition will have a positive impact on synthetic chemistry.
ISSN:1420-3049

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