Examination of Phosphorus Hyperfine Coupling Constants in Nitroaromatic Anion Radicals<sup>1a</sup>

Gulick, Wilson M.; Geske, David H.

doi:10.1021/ja00965a009

Cited by 63 publications

(29 citation statements)

References 4 publications

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“…The substrate bis‐ p ‐nitrophenyl phosphate sodium salt (BPNPP) was an Aldrich product, used as received. The substrate p ‐nitrophenyl diphenylphosphate (PNPDPP) was synthesised by following a reported procedure . All kinetics were performed under pseudo‐first‐order conditions with excess of catalyst over substrate.…”

Section: Methodsmentioning

confidence: 99%

Distance between Metal Centres Affects Catalytic Efficiency of Dinuclear Co^III Complexes in the Hydrolysis of a Phosphate Diester

et al. 2018

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Dinuclear CoIII complex catalysed hydrolysis of bis‐p‐nitrophenylphosphate, a DNA model substrate, is reported. The catalysts were designed in such a way that the two CoIII ions cannot be contemporaneously involved in the complexation of the substrate or transition state. Experimental evidence of the involvement of such a remote metal centre in the catalysis of the hydrolysis of a phosphate diester is provided. This contribution amounts to a ca. 64‐fold rate acceleration for the second‐order rate constants of the best dinuclear complex over the mononuclear one, which is apparently due to general acid or H‐bonding catalysis. Furthermore, there is significant distance dependence for this catalytic contribution and, in this case, it appears that the best distance (as estimated by DFT calculations) is ca. 7.7 Å. This may indicate that the presence of metal centres in close proximity, as required for mechanism proposals in which all metals are directly involved in transition‐state coordination, is not the only option for rate acceleration in natural phosphate hydrolysis.

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Section: Methodsmentioning

confidence: 99%

Distance between Metal Centres Affects Catalytic Efficiency of Dinuclear Co^III Complexes in the Hydrolysis of a Phosphate Diester

et al. 2018

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“…33 PNPDPP was prepared and purified by literature methods. 34 pKa Determination. The apparent pKa of the micellar CTACl-bound MPP was determined from the rate-constant vs. pH plots for the cleavages of 1 × 10 -5 M PNPDPP by 4 × 10 -5 M MPP in 1 × 10 -3 M micellar CTACl, 0.02 phosphate buffer, at 25 ( 1°C.…”

Section: Methodsmentioning

confidence: 99%

Evidence for the Formation of Acylated or Phosphorylated Monoperoxyphthalates in the Catalytic Esterolytic Reactions in Cationic Surfactant Aggregates

Bhattacharya

Snehalatha

1997

J. Org. Chem.

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Monoperoxyphthalate (MPP) was solubilized in three different aqueous cationic surfactant aggregates composed of (i) a micellar cetyltrimethylammonium chloride (CTACl) solution; (ii) an oil-in-water (O/W) microemulsion (ME) stabilized by CTACl, and a cosurfactant, tert-butyl alcohol, and (iii) a vesicular medium composed of dispersions of dihexadecyldimethylammonium chloride (DHDAC). At pH approximately 8.5 and 25 degrees C, each of these formulations was used to cleave p-nitrophenyl diphenyl phosphate (PNPDPP). The aggregate and the maximum pseudo-first-order rate constants ([MPP] = 4 x 10(-)(5) M, and [PNPDPP] = 1 x 10(-)(5) M) for the PNPDPP cleavages are the following: buffer alone, 0.00034 s(-)(1); micelle: 0.024 s(-)(1); ME: 0.0048 s(-)(1); and vesicle: 0.025 s(-)(1). Importantly all the catalytic formulations showed "turnover" behavior in the presence of excess substrates. By the combined use of (1)H- and (31)P-NMR spectrometry and synthesis, it was possible to provide evidence for the formation of acylated or phosphorylated monoperoxypthalates in the catalytic hydrolyses in cationic surfactant aggregates.

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“…The interaction decreases in the order of para > ortho > meta. 16 Allen et al 24 and Gulick et al 25 have, in fact, rationalized the coupling constant in a series of semiquinone phosphate radicals in terms of a hyperconjugative mechanism.…”

Section: Introductionmentioning

confidence: 99%

Dependence of the long‐range phosphorus–hydrogen coupling constant ⁿJ_P–H (n = 3,6,7) on the bond order between phosphorus and its substituents: preparation and spectroscopic characterization of several phosphoramidates

Gholivand

Ghadimi

Naderi‐Manesh

et al. 2001

Magnetic Reson in Chemistry

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The examination of spectra of a selected series of phosphoramidates showed that, in addition to a double bond, whenever there are one or two partial multiple bonds in the molecule the long-range coupling constant, such as 6 J P -H , 7 J P -H and 3 J P -H , either disappears or at least reduces. In particular, the experimental data indicate the unexpected effect of a partial multiple bond between phosphorus and fluorine in 7 J P -H and 3 J P -H .

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Examination of Phosphorus Hyperfine Coupling Constants in Nitroaromatic Anion Radicals^1a

Cited by 63 publications

References 4 publications

Distance between Metal Centres Affects Catalytic Efficiency of Dinuclear Co^III Complexes in the Hydrolysis of a Phosphate Diester

Distance between Metal Centres Affects Catalytic Efficiency of Dinuclear Co^III Complexes in the Hydrolysis of a Phosphate Diester

Evidence for the Formation of Acylated or Phosphorylated Monoperoxyphthalates in the Catalytic Esterolytic Reactions in Cationic Surfactant Aggregates

Dependence of the long‐range phosphorus–hydrogen coupling constant ⁿJ_P–H (n = 3,6,7) on the bond order between phosphorus and its substituents: preparation and spectroscopic characterization of several phosphoramidates

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Examination of Phosphorus Hyperfine Coupling Constants in Nitroaromatic Anion Radicals1a

Cited by 63 publications

References 4 publications

Distance between Metal Centres Affects Catalytic Efficiency of Dinuclear CoIII Complexes in the Hydrolysis of a Phosphate Diester

Distance between Metal Centres Affects Catalytic Efficiency of Dinuclear CoIII Complexes in the Hydrolysis of a Phosphate Diester

Evidence for the Formation of Acylated or Phosphorylated Monoperoxyphthalates in the Catalytic Esterolytic Reactions in Cationic Surfactant Aggregates

Dependence of the long‐range phosphorus–hydrogen coupling constant nJP–H (n = 3,6,7) on the bond order between phosphorus and its substituents: preparation and spectroscopic characterization of several phosphoramidates

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Examination of Phosphorus Hyperfine Coupling Constants in Nitroaromatic Anion Radicals^1a

Distance between Metal Centres Affects Catalytic Efficiency of Dinuclear Co^III Complexes in the Hydrolysis of a Phosphate Diester

Distance between Metal Centres Affects Catalytic Efficiency of Dinuclear Co^III Complexes in the Hydrolysis of a Phosphate Diester

Dependence of the long‐range phosphorus–hydrogen coupling constant ⁿJ_P–H (n = 3,6,7) on the bond order between phosphorus and its substituents: preparation and spectroscopic characterization of several phosphoramidates