Structure sensitivity of the Marcus .lambda. for hydride transfer between NAD+ analogs

Kreevoy, Maurice M.; Ostovic, Drazen; Lee, In Sook Han; Binder, David A.; King, G. W.

doi:10.1021/ja00210a036

Cited by 85 publications

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“…The current relationship of eq. [4] appears to be the first reported for a common donor with a series of different acceptors, and also is the most extensive quantitative relationship of this type of which we are aware. Since Mulliken's ideas form the basis of most modem theoretical considerations of charge-transfer complexation (44,45), a rationalization of this divergence between theory and experimental result is essential.…”

Section: Benzylogous Heteroaromatic Cationsmentioning

confidence: 74%

“…McGlynn (40) has commented upon this situation in detail, and we note this commonly observed trend is also reproduced by the data from our current study, and is expressed by eq. [4] above. The only earlier attempt at such a quantitative relationship seems to be the report of Tamres et al (41) who found that E,,, is linearly dependent upon ~/FK for the association of a series of five methylbenzenes with molecular iodine.…”

Section: Benzylogous Heteroaromatic Cationsmentioning

confidence: 95%

“…The current data, and in particular eq. [4], will now be considered briefly in the context of each of these hypotheses.…”

Section: Benzylogous Heteroaromatic Cationsmentioning

confidence: 99%

“…In general, one would expect (2)(3)(4) that the reaction of eq. [ l ] would be preceded by the formation of an association complex between A+ and DH, and a minimal description of such reactions would be that shown in Scheme From the observation of saturation kinetics for pseudo-firstorder rate constants for reactions of the type shown in eq.…”

mentioning

confidence: 99%

“…To a first approximation, one may characterize the [A+.DH] association complex as a charge-transfer complex between the D H electron donor and the A + acceptor (4). In fact, the formation of a charge-transfer complex between 1-benzyl-1,4-dihydronicotinamide (1) and the 10-methylacridinium cation (2) has been spectroscopically observed (5).…”

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confidence: 99%

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Charge transfer complexation of N,N-dimethyl-p-toluidine with nitrogen heteroaromatic cations as a model for association complexes in hydride transfer reactions

Bunting¹,

Luscher²

1988

Can. J. Chem.

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Can. J. Chem. 66, 2532. Charge-transfer complexation of N,N-dimethyl-p-toluidine (DMT) with each of the following N-methyl cations has been investigated in acetonitrile solution at 25OC: acridinium; phenanthridinium; 3-X-quinolinium and 4-X-isoquinolinium (X = H, Br, CONH2, CN); 5-nitroisoquinolinium; 3-X-pyridinium (X = CONH2, CN) (also the N-benzyl pyridinium cations); N,N1-dimethyl-4,4'-dipyridylium dication. Charge-transfer absorption maxima are reported, and extinction coefficients ( E , , , ) at these maxima and association constants (K) for 1:l complex formation have been evaluated from the dependence of absorbance upon [DMT]. In general, the longest wavelength absorption maximum increases with increasing association constant. There is a strictly linear relationship between E, , , and 1/K. These observations are considered in the context of theories of charge-transfer spectra. Such charge-transfer species are considered as models for the association complexes that are believed to exist upon the reaction pathway for hydride transfer between heteroaromatic cations. Although some significant qualitative relationships are apparent, variations in susceptibility of heteroaromatic cations to charge-transfer complexation are much smaller than variations in the reactivity of these cations towards hydride donor species. i. ces maxima ainsi que les constantes d'association (K) pour la formation des complexes 1 :l. I1 existe une relation strictement lintaire entre le E , , , et 1 /K. On considkre ces observations dans le contexte des thCories des spectres de transfert de charge. On considkre que de telles esp6ces de transfert de charge sont de bons modkles pour les complexes d'association qui existeraient lors du cheminement rtactionnel des hydrures au cours de leur transfert entre des cations hCtCroaromatiques. MCme s'il semble exister des relations qualitatives importantes, les variations dans la susceptibilitk des cations hCtCroaromatiques i. la complexation de transfert de charge sont beaucoup plus faibles que les variations observkes dans la rCactivitC de ces cations vis-a-vis des espkces donneurs d'hydrure.[Traduit par la revue]

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Section: Benzylogous Heteroaromatic Cationsmentioning

confidence: 74%

Section: Benzylogous Heteroaromatic Cationsmentioning

confidence: 95%

“…The current data, and in particular eq. [4], will now be considered briefly in the context of each of these hypotheses.…”

Section: Benzylogous Heteroaromatic Cationsmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Charge transfer complexation of N,N-dimethyl-p-toluidine with nitrogen heteroaromatic cations as a model for association complexes in hydride transfer reactions

Bunting¹,

Luscher²

1988

Can. J. Chem.

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Kinetik der Hydrid‐Übertragungen von CH‐, SiH‐, GeH‐ und SnH‐Gruppen auf Carbenium‐Ionen

Mayr

Basso

1992

Angewandte Chemie

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Kinetics of Hydride Transfers from CH, SiH, GeH, and SnH Groups to Carbenium Ions

Mayr

Basso

1992

Angew. Chem. Int. Ed. Engl.

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and carbon-centered "multiple warhead" tetraradical 10, a potentially powerful species for DNA damage. In the event, however, none of the products expected to arise from 10 were formed. Instead, the two novel dihydroperoxides 8 and 9 were isolated in 22 and 10% yield, respectively. The same transformations were also effected, although less cleanly, by thermolysis in the presence of hydrogen atom donors. Quite intriguing is the possibility of the intermediacy of a dioxetener'] which is presumed to eject the equivalent of ethenedione,"] perhaps as two carbon monoxide molecules.[91 Compounds2 and 3 caused significant DNA cleavage when incubated with +XI74 supercoiled DNA at pH 8.5 and 50 "C (Fig. 2). Interestingly, dione 4 caused only slight DNA damage under the same conditions, whereas hydroperoxides 8 and 9 showed, as expected, quite strong DNA-cleaving activities. Based on the chemistry of these systems we presume that whereas the ten-membered ring enediynes 2 and 3 may exert their DNA-cleaving power by cyclization to an aromatic diradical, the open-chain enediynes 8 and 9 may operate by an entirely different mechanism involving the generation of oxygen-centered radicals.

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Structure sensitivity of the Marcus .lambda. for hydride transfer between NAD+ analogs

Cited by 85 publications

References 0 publications

Charge transfer complexation of N,N-dimethyl-p-toluidine with nitrogen heteroaromatic cations as a model for association complexes in hydride transfer reactions

Charge transfer complexation of N,N-dimethyl-p-toluidine with nitrogen heteroaromatic cations as a model for association complexes in hydride transfer reactions

Kinetik der Hydrid‐Übertragungen von CH‐, SiH‐, GeH‐ und SnH‐Gruppen auf Carbenium‐Ionen

Kinetics of Hydride Transfers from CH, SiH, GeH, and SnH Groups to Carbenium Ions

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