The successful applications of Marcus theory to catalysis by labile metal ions in the base-catalyzed enolization and decarboxylation of oxalacetate and in the ketonization and condensation of enolpyruvate are described. Illustrations are presented describing the prediction of rate constants and the use of the theory in original and expanded versions to gain insight into possible features of a reaction mechanism.

A yellow, solid, ion-dipole charge transfer complex, [M][B10H14I], is formed upon mixing the solids [M]I (M = [N(n-(C4H9)(4)](+), [P(C6H5)(3)CH3](+), [(Ph(3)P)(2)N](+)) and B10H14. The [B10H14I](-) ion is stabilized in the solid state by the presence of bulky cations; B10H14 cannot be separated by sublimation from the solid. A Job continuous variations experiment establishes that the reaction stoichiometry, a 1:1 molar ratio of [N(n-(C4H9)(4)]I to B10H14, also occurs in CH2Cl2 solution. While there is no apparent reaction when solid alkali metal iodides are mixed with B10H14 in the absence of a solvent, addition of an appropriate solvent to the solid mixture causes formation of the [B10H14I](-) anion. However, removal of the solvent causes the complex to revert to a mixture from which B10H14 can be removed by sublimation. When 2,4-I2B10H12 is mixed with iodide salts of the cations [N(n-C4H9)(4)](+) [P(C6H5)(3)CH3](+), [(Ph(3)P)(2)N](+), Na+, and K+ in the absence of a solvent, there is no apparent reaction. However when a suitable solvent is present, the complex anion [2,4-I2B10H12I](-) is formed. A single crystal X-ray structure determination of [P(C6H5)(3)CH3][2,4-I2B10H12I] shows the unique iodide residing on top of the four hydrogen bridge atoms and the 6,9 boron atoms at the opening of the B-10 basket. Crystal data for [P(C6H5)(3)CH3][2,4-I2B10H12I]: monoclinic P2(1)/c, a = 12.868(4) Angstrom, b = 10.562(3) Angstrom, c = 22.007(8) Angstrom, beta = 99.40(2)degrees, Z = 4, V = 2950.7 Angstrom(3), R = 3.3%, R(w) = 3.6%.

The picket fence porphyrin, Fe(III)(meso-alpha,alpha,alpha,alpha-tetrakis[o-(N-methylisonicotinamido)phenyl]porphyrin), alpha4-Fe(III)(TMINP)5+, shows two proton ionization steps in the pH regions commonly observed for water soluble Fe(III) porphyrins: pK1a = 6.1; pK2a = 10.0. alpha4-Fe(III)(TMINP)(OH)4+ is found to have a considerably lower tendency to dimerize than the previously reported isomeric Fe(III)(OH)(meso-alpha,alpha,alpha,alpha-tetrakis[o-(N-methylnicotinamido)phenyl] porphyrin)4+, alpha4-Fe(III)(TMNP)(OH)4+.10 The difference in dimer stabilities is attributed to the higher concentration of positive charge around Fe(III) in the isonicotinamido isomer. Fe(III)(meso-tetrakis[N-methylpyridinium-4-yl] porphyrin)5+, Fe(III)(TMPyP)5+, and alpha4-Fe(III)(TMINP)5+ form very stable Fe(III)(porph)(CN)23+ complexes that in alkaline solutions are fully formed at millimolar excesses of CN-. The stability constant for the latter dicyanoporphyrin complex is higher than that for the former, again a manifestation of the higher positive charge near the metal ion of the picket fence porphyrin. Fe(III)(TMPyP)(CN)23+ has a sufficiently positive reduction potential that it is easily, but slowly, reduced to Fe(II)(TMPyP)(CN)22+ by slight excesses of CN-. Alpha4-Fe(III)(TMINP)(CN)23+ is not reduced by CN-. The carbon dioxide radical anion, C02-, reduces Fe(III)(TMPyP)5+ and a4-Fe(III)(TMINP)5+ at diffusion-controlled rates with a steric factor contributing to a slightly smaller rate constant in the case of the picket fence porphyrin. Rates of reduction by the superoxide radical, O2-, are less than diffusion controlled with rate constants for the reactions of Fe(III)(TMPyP)5+, alpha3beta-Fe(III)(TMINP)5+ and Fe(III)(TPPS4)3- (tetra(4-sulfonatophenyl)porphyrin) following their E1/2 valUes in accordance with the Marcus equation. A high rate constant for alpha4-Fe(III)(TMINP)5+ reduction implicates a different reaction mechanism that is postulated to involve the prebinding Of O2- within the pocket formed by the porphin ring substituents.

Rates of exchange of (CO)-C-13 gas (0.1-6.0 atm) with (CO)-C-12 in [HM3(CO-12)11]- and [DM3(CO-12)11]- (M = Ru, Os) were determined. The appearance of (CO)-C-12 in the gas phase above tetrahydrofuran solutions of the cluster salts was monitored by IR spectroscopy as a function of time. Overall (CO)-C-13-(CO)-C-12 exchange occurs by two parallel pathways. A dissociative pathway, which is first order in anion and zero order in CO, dominates the exchange process. As the concentration of (CO)-C-13 is increased, an associative step that is first order in cluster anion and first order in CO becomes increasingly significant. Exchange reactions involving [HRu3(CO)11]- are faster than those involving [HOs3(CO)11]-. With increased ion-pairing ability of the counterion of [HRu3(CO)11]-, the rate of exchange increases (PPN+ congruent-to PPh4+ < NEt4+ < K+ < Na+ < Li+), affecting, principally, the dissociative step. Similar results are observed for [HOs3(CO)11]- (PPh4+ < NEt4+ < K+ congruent-to Na+). Addition of BH3 increases the rate of exchange through the dissociative pathway. The associative pathway of exchange is related to the activation of hydride in these cluster anions when under water-gas shift reaction conditions. Examination of (CO)-C-13 exchange with (CO)-C-12 in the salts [X][HM3(CO)11] ([X] = Na+, [PPh4]+; M = Ru, Os) and [X][DM3(CO)11] ([X] = Na+, [PPh4]+; M = Ru, Os) reveals a kinetic isotope effect for the associative step, k2(H)/k2(D) = 1.4-1.8, which can be related to the displacement by CO of the bridging to a terminal site.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTransimination kinetics of pyridoxal 5'-phosphate Schiff basesShu Huan Weng and Daniel L. LeussingCite this: J. Am. Chem. Soc. 1983, 105, 12, 4082–4090Publication Date (Print):June 1, 1983Publication History Published online1 May 2002Published inissue 1 June 1983https://doi.org/10.1021/ja00350a056RIGHTS & PERMISSIONSArticle Views223Altmetric-Citations16LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (1004 KB) Get e-Alerts Get e-Alerts

ADVERTISEMENT RETURN TO ISSUEPREVBook and Media Revie...Book and Media ReviewThe lewis acid-base concepts: an overviewDaniel L. Leussing Cite this: J. Chem. Educ. 1982, 59, 5, A179Publication Date (Print):May 1, 1982Publication History Received3 August 2009Published online1 May 1982Published inissue 1 May 1982https://doi.org/10.1021/ed059pA179.2RIGHTS & PERMISSIONSArticle Views628Altmetric-Citations2LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (2 MB) Get e-Alerts Get e-Alerts

The ZnII-catalysed rate of formation of pyruvate dimer(parapyruvate) is enhanced by the decarboxylation of oxac2–, providing evidence for the postulated existence of intermediate pyruvate enolate in both of these reactions.

ADVERTISEMENT RETURN TO ISSUEPREVBook and Media Revie...Book and Media ReviewEquilibrium: A chemistry of solutions (Balckburn, Thomas R.)Daniel L. Leussing Cite this: J. Chem. Educ. 1971, 48, 3, A224Publication Date (Print):March 1, 1971Publication History Received3 August 2009Published online1 March 1971Published inissue 1 March 1971https://doi.org/10.1021/ed048pA224RIGHTS & PERMISSIONSArticle Views168Altmetric-Citations-LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (8 MB) Get e-Alerts Get e-Alerts

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTKinetics of formation of N-pyruvylideneglycinatozinc(II). Zinc(II) catalysis under approximately neutral conditionsDaniel L. Leussing and Larry AndersonCite this: J. Am. Chem. Soc. 1969, 91, 17, 4698–4700Publication Date (Print):August 1, 1969Publication History Published online1 May 2002Published inissue 1 August 1969https://pubs.acs.org/doi/10.1021/ja01045a018https://doi.org/10.1021/ja01045a018research-articleACS PublicationsRequest reuse permissionsArticle Views28Altmetric-Citations4LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTChlorophyll-ligand interactions from nuclear magnetic resonance studiesJoseph J. Katz, Harold H. Strain, Daniel L. Leussing, and Ralph C. DoughertyCite this: J. Am. Chem. Soc. 1968, 90, 3, 784–791Publication Date (Print):January 1, 1968Publication History Published online1 May 2002Published inissue 1 January 1968https://doi.org/10.1021/ja01005a041RIGHTS & PERMISSIONSArticle Views125Altmetric-Citations49LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (968 KB) Get e-Alerts Get e-Alerts

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTN-Salicylideneglycinato complexes. Comparison with pyridoxalDaniel L. Leussing and Kyu Sun. BaiCite this: Anal. Chem. 1968, 40, 3, 575–581Publication Date (Print):March 1, 1968Publication History Published online1 May 2002Published inissue 1 March 1968https://pubs.acs.org/doi/10.1021/ac60259a019https://doi.org/10.1021/ac60259a019research-articleACS PublicationsRequest reuse permissionsArticle Views128Altmetric-Citations34LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTKinetics of formation of N-salicylideneglycinatonickel-(II), -copper(II), and -zinc(II). Elucidation of the template mechanismsKyu Sun. Bai and Daniel L. LeussingCite this: J. Am. Chem. Soc. 1967, 89, 24, 6126–6130Publication Date (Print):November 1, 1967Publication History Published online1 May 2002Published inissue 1 November 1967https://doi.org/10.1021/ja01000a021RIGHTS & PERMISSIONSArticle Views89Altmetric-Citations19LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (519 KB) Get e-Alerts Get e-Alerts

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSpectrophotometric Study of the Bleaching of Ferric ThioglycolateDaniel L. Leussing and Leonard NewmanCite this: J. Am. Chem. Soc. 1956, 78, 3, 552–556Publication Date (Print):February 1, 1956Publication History Published online1 May 2002Published inissue 1 February 1956https://doi.org/10.1021/ja01584a010RIGHTS & PERMISSIONSArticle Views74Altmetric-Citations30LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (613 KB) Get e-Alerts Get e-Alerts