Structure of triphenylphosphine oxide hemiperhydrate

Thierbach, D.; Huber, F.; Preut, H.

doi:10.1107/s0567740880005067

Cited by 26 publications

(18 citation statements)

References 10 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…(Ph 3 P=O) 2 •H 2 O 2 was synthesized according to literature protocols, and its identity and purity were verified by 1 H-NMR and Elemental analysis. 12 Synthesis and manipulations of copper salts were performed according to standard Schlenk techniques or in an MBraun glovebox (with O 2 and H 2 O levels below 1 ppm). Carbon monoxide (CO) gas was obtained from Airgas and passed through an oxygen and moisture scrubbing column.…”

Section: Methodsmentioning

confidence: 99%

Amine Oxidative N-Dealkylation via Cupric Hydroperoxide Cu-OOH Homolytic Cleavage Followed by Site-Specific Fenton Chemistry

et al. 2015

View full text Add to dashboard Cite

Copper(II)-hydroperoxide species are significant intermediates in processes such as fuel cells and (bio)chemical oxidations, all involving stepwise reduction of molecular oxygen. We previously reported a CuII-OOH species that performs oxidative N-dealkylation on a dibenzylamino group that is appended to the 6-position of a pyridyl donor of a tripodal tetradentate ligand. To obtain insights into the mechanism of this process, reaction kinetics and products were determined employing ligand substrates with various para- substituent dibenzyl pairs (-H,-H; -H,-Cl; -H,-OMe and -Cl,-OMe), or with partially or fully deuterated dibenzyl N-(CH2Ph)2 moieties. A series of ligand-copper(II) bis-perchlorate complexes were synthesized, characterized, and the X-ray structures of the -H, -OMe analog was were determined. The corresponding metastable CuII-OOH species were generated by addition of H2O2/base in acetone at –90 °C. These convert (t1/2 ~ 53 s) to oxidatively N-dealkylated products, producing para-substituted benzaldehydes. Based on the experimental observations and supporting DFT calculations, a reaction mechanism involving dibenzylamine H-atom abstraction or electron-transfer oxidation by the CuII-OOH entity could be ruled out. It is concluded that the chemistry proceeds by rate limiting Cu–O homolytic cleavage of the CuII–(OOH) species, followed by site-specific copper Fenton chemistry. As a process of broad interest in copper as well as iron oxidative (bio)chemistries, a detailed computational analysis was performed, indicating that a CuIOOH species undergoes O–O homolytic cleavage to yield a hydroxyl radical and CuIIOH rather than heterolytic cleavage to yield water and a CuII-O•−.

show abstract

Section: Methodsmentioning

confidence: 99%

Amine Oxidative N-Dealkylation via Cupric Hydroperoxide Cu-OOH Homolytic Cleavage Followed by Site-Specific Fenton Chemistry

et al. 2015

View full text Add to dashboard Cite

show abstract

“…3a-3c). Compounds BAFGOH (Ahn et al, 2015), BAFJUQ (Ahn et al, 2015), VANVOX (Hilliard et al, 2012) and XETSUK (Č ermá k et al, 2001) belong to type a [R 2 4 (10)]; compounds EKULUR (Chandrasekaran et al, 2002), TPPOPH (Thierbach et al, 1980) and UKEFEV (Sevcik et al, 2003)…”

Section: Figurementioning

confidence: 99%

Crystal structure of (Z)-N-benzylidene-1-phenylmethanamine oxide hydrogen peroxide monosolvate

et al. 2017

View full text Add to dashboard Cite

The title adduct, C14H13NO·H2O2, consists of (Z)-N-benzylidene-1-phenylmethanamine oxide and hydrogen peroxide molecules in a 1:1 ratio. The organic coformer adopts a skew geometry with an inter-aryl-ring dihedral angle of 81.9 (2)°. In the crystal, the organic and peroxide molecules are linked through both peroxide O—H donor groups to oxide O-atom acceptors, giving one-dimensional chains extending along thebaxis. Present also are weak intermolecular C—H...O hydrogen-bonding interactions.

show abstract

“…We have shown for a wide range of compounds that two donor hydrogen bonds were the minimal number of interactions for organic peroxosolvates [12][13][14][15][16]. Thus, only two H-bonds formed by peroxide molecules were observed in the structures of Ph 4 X + Hal -·2(H 2 O 2 ) (X = P, As; Hal = Cl, Br) [6] and phosphine oxide peroxosolvates [17,18], wherein the peroxide hydrogen atoms were the only active hydrogen atoms. Usually, if a crystal contained other than peroxo active hydrogen atoms, H 2 O 2 molecules additionally formed one, two, or three acceptor hydrogen bonds [12-14, 16, 19-23].…”

mentioning

confidence: 85%

Crystal structure of ammonium succinate peroxosolvate

et al. 2014

View full text Add to dashboard Cite

The crystal structure of previously unknown ammonium succinate peroxosolvate is studied. It is shown that it represents a rare example of the structure where H 2 O 2 molecule forms two donor hydrogen bonds and does participate in any acceptor hydrogen bonds, despite the presence of substantial quantity of nonperoxide active hydrogen atoms.Peroxosolvates are molecular adducts of hydrogen peroxide with various inorganic and organic compounds. Several of them are widely used in industry, household chemistry and medicine as solid and stable enough sources of hydrogen peroxide in bleaching and disinfection processes. Annual world production of Na 2 CO 3 ·1.5H 2 O 2 and urea peroxosolvates CH 4 N 2 O · H 2 O 2 has risen to hundreds of thousands tons [1].For the first time peroxosolvates of organic compounds were obtained by S. Tanatar in 1908 [2]. He synthesized and established the composition of urea peroxosolvate. That compound immediately attracted great attention both from theoretical and practical points of view. Its crystal structure was completely determined by X-ray diffraction as early as in 1941 [3]. Until quite recently, urea peroxosolvate remains the target of intensive research [4][5][6]. In [2], another peroxosolvate of a simple organic compound was obtained, namely peroxosolvate of succinimide. It was crystallized by slow evaporation of the solution of succinimide in 30% Н 2 О 2 at 50°С. The composition (C 4 H 5 NO 2 ·H 2 O 2 ) was established by permanganatometric titration of the included peroxide [2]. Surprisingly, we did not find any mentions about this compound in the later literature. We made systematic attempts to crystallize this compound from saturated (at r.t.) solutions of succinimide in hydrogen peroxide of various concentrations (30%, 50%, 70% and 96%) by cooling down to +5 °C, -12 °C and -18 °С. However, in all trials the resulting crystals were nothing else but the starting succinimide, as it was shown by X-ray diffraction.It is known that cyclic imides undergo hydrolytic degradation in acidic media resulting in a range of products [7]: Scheme 1.

show abstract

Structure of triphenylphosphine oxide hemiperhydrate

Cited by 26 publications

References 10 publications

Amine Oxidative N-Dealkylation via Cupric Hydroperoxide Cu-OOH Homolytic Cleavage Followed by Site-Specific Fenton Chemistry

Amine Oxidative N-Dealkylation via Cupric Hydroperoxide Cu-OOH Homolytic Cleavage Followed by Site-Specific Fenton Chemistry

Crystal structure of (Z)-N-benzylidene-1-phenylmethanamine oxide hydrogen peroxide monosolvate

Crystal structure of ammonium succinate peroxosolvate

Contact Info

Product

Resources

About