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Keypour, Hassan; Dehdari, A; Salehzadeh, Sadegh; Wainwright, Kevin P.

doi:10.1023/a:1023670918923

Cited by 21 publications

(11 citation statements)

References 13 publications

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“…The following results were obtained from the study of proton microaffinities and the calculation of the first proton macroaffinity of the metal complexes using eqs 10−12: (1) For all complexes, the smallest calculated proton microaffinity is related to the amine group on the coordinated ethylene arm, and the greatest one is related to the amine group on the butylene arm (see Table ). This is consistent with the fact that seven-membered chelate rings are less stable than six-membered rings and that both are less stable than five-membered chelate rings. , (2) As can be seen in Table , the smallest proton macroaffinity is calculated for the [Zn(tren)] 2+ complex. In fact, the order of the first proton macroaffinity for the Zn 2+ complexes is [ Zn(tren)] 2+ < [Zn(pee)] 2+ < [Zn(ppe)] 2+ < [Zn(tpt)] 2+ < [Zn(ppb)] 2+ .…”

Section: Resultssupporting

confidence: 82%

First Reported Correlation between the Calculated Gas-Phase Proton Macroaffinities of Some Metal Complexes with Their Measured Formation Constants in Solution: Zn(II) Complexes of a Series of Tripodal Aliphatic Tetraamines

2008

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A theoretical study on the first protonation step of a series of metal complexes with the general formula {M(N[(CH2)nNH2][(CH2)mNH2][(CH2)pNH2])2+} (n = m = p = 2, tren; n = 3, m = p = 2, pee; n = m = 3, p = 2, ppe; n = m = p = 3, tpt; n = 2, m = 3, p = 4, epb; and n = m = 3, p = 4, ppb; and M = Zn2+) was reported using both the Hartree-Fock and DFT (B3LYP) levels of theory. For the first time, two kinds of our recently published definitions for gas-phase proton affinities of polybasic ligands, proton microaffinity and proton macroaffinity, were extended to their metal complexes. There is a good correlation between the calculated gas-phase proton macroaffinities and the corresponding formation constants in solution.

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Section: Resultssupporting

confidence: 82%

First Reported Correlation between the Calculated Gas-Phase Proton Macroaffinities of Some Metal Complexes with Their Measured Formation Constants in Solution: Zn(II) Complexes of a Series of Tripodal Aliphatic Tetraamines

2008

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“…Therefore the present results are completely consistent with this fact that six-membered chelate rings are less stable than fivemembered chelate rings. 14,15 This journal is © The Royal Society of Chemistry 2009 a The data in parentheses are calculated using LanL2DZ basis set. b 2,2; 2,3 and 3,3 correspond to a secondary amine located between two ethylene arms, one ethylene and one propylene arm or two propylene arms, respectively.…”

Section: Resultsmentioning

confidence: 99%

Theoretical studies on the first proton macroaffinity of Ni(ii), Cu(ii), Zn(ii) and Cd(ii) complexes of four triazacycloalkanes ([X]ane N3, X = 9–12): good correlations with the formation constants in solution

Salehzadeh¹,

Shooshtari²,

Bayat³

2009

Dalton Trans.

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A theoretical study on the first protonation step of Ni(ii), Cu(ii), Zn(ii) and Cd(ii) complexes of some triazacycloalkanes with general formula [X]ane N(3) (X = 9-12) is reported. The calculations were performed at DFT (B3LYP) level of theory, using LanL2DZ basis set. The DFT calculations were performed again using DZVP2 basis set for Ni(ii), Cu(ii) and Zn(ii) complexes and DZVP for Cd(ii) complexes. Once again, two kinds of our recently published definitions for gas-phase proton affinities of polybasic ligands, proton microaffinity and proton macroaffinity, were extended to their metal complexes. Among the 16 investigated complexes the most stable complex has both the smallest proton macroaffinity and macrobasicity. The least stable complex has also both the greatest proton macroaffinity and macrobasicity. In the case of each metal ion there are good correlations between the calculated gas-phase proton macroaffinities as well as macrobasicities of the corresponding complexes with their formation constants in solution.

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“…[22][23][24][25][26] Second, the formation constants of both the latter complexes and their protonated form have been reported in the literature. 27 Third, the molecular structures and correct formulations for a number of present metal complexes and their protonated form have been determined by X-ray crystal structure analysis. [28][29][30] Thus, we can easily study the degree of agreement between our theoretical results and the experimental data.…”

Section: Introductionmentioning

confidence: 99%

Theoretical studies on the structure and protonation of Cu(II) complexes of a series of tripodal aliphatic tetraamines: Good correlations with the experimental data

Salehzadeh

Bayat

2010

J Comput Chem

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DFT(B3LYP) studies on first protonation step of a series of Cu(II) complexes of some tripodal tetraamines with general formula N[(CH(2))(n)NH(2)][(CH(2))(m)NH(2)][(CH(2))(p)NH(2)] (n = m = p = 2, tren; n = 3, m = p = 2, pee; n = m = 3, p = 2, ppe; n = m = 3, tpt; n = 2, m = 3, p = 4, epb; and n = m = 3, p = 4; ppb) are reported. First, the gas-phase proton macroaffinity of all latter complexes was calculated with considering following simple reaction: [Cu(L)](2+)(g) + H(+)(g) --> [Cu(HL)](3+)(g). The results showed that there is a good correlation between the calculated proton macroaffinities of all complexes with their stability constants in solution. Then, we tried to determine the possible reliable structures for microspecies involved in protonation process of above complexes. The results showed that, similar to the solid state, the [Cu(L)(H(2)O)](2+) and [Cu(HL)(H(2)O)(2)](3+) are most stable species for latter complexes and their protonated form, respectively, at gas phase. We found that there are acceptable correlations between the formation constants of above complexes with both the -Delta E and -Delta G of following reaction: [Cu(L)(H(2)O)](2+)(g) + H(+)(g) + H(2)O(g) --> [Cu(HL)(H(2)O)(2)](3+)(g). The -Delta E of the latter reaction can be defined as a theoretically solvent-proton macroaffinity of reactant complexes because they have gained one proton and one molecule of the solvent. The unknown formation constant of [Cu(epb)](2+) complex was also predicted from the observed correlations. In addition, the first proton affinity of all complexes was studied in solution using DPCM and CPCM methods. It was shown that there is an acceptable correlation between the solvent-proton affinities of [Cu(L)(H(2)O)](2+) complexes with formation constants of [Cu(HL)(H(2)O)(2)](3+) complexes in solution.

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Untitled

Cited by 21 publications

References 13 publications

First Reported Correlation between the Calculated Gas-Phase Proton Macroaffinities of Some Metal Complexes with Their Measured Formation Constants in Solution: Zn(II) Complexes of a Series of Tripodal Aliphatic Tetraamines

First Reported Correlation between the Calculated Gas-Phase Proton Macroaffinities of Some Metal Complexes with Their Measured Formation Constants in Solution: Zn(II) Complexes of a Series of Tripodal Aliphatic Tetraamines

Theoretical studies on the first proton macroaffinity of Ni(ii), Cu(ii), Zn(ii) and Cd(ii) complexes of four triazacycloalkanes ([X]ane N3, X = 9–12): good correlations with the formation constants in solution

Theoretical studies on the structure and protonation of Cu(II) complexes of a series of tripodal aliphatic tetraamines: Good correlations with the experimental data

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