Coordination reactions in non aqueous solutions - The role of the donor strength

Gutmann, V.; Wychera, Erhard

doi:10.1016/0020-1650(66)80056-9

Cited by 390 publications

(115 citation statements)

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Section: Introductionmentioning

confidence: 99%

“…As a result, some linear functions with few parameters for description of the solvent effect have been proposed. [24][25][26] The most interesting function is that proposed by Kamlet and Taft. The formation constants of the species formed in the systems H + + thallium(I) + AMP and H + + AMP have been determined in aqueous solutions of methanol at 25˚C and constant ionic strength 0.1 mol dm -3 sodium perchlorate, using spectrophotometric and potentiometric techniques.…”

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confidence: 99%

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Complexation of Thallium(I) with Adenosine 5′-Monophosphate in Aqueous Methanol Solutions

2005

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The development of various kinds of approaches to hydrophobic hydration is necessary for a better understanding of its key role in controlling biochemical processes in water. 1,2 In the last few years, several experimental and theoretical works dealing with the effect of solvent on many reactions have been published. [3][4][5] Most of these papers are concerned with the effect of solvent on reaction rates. There is surprisingly little work, involving the effect of solvent on the thermodynamics and complexation of some biologically important ligands. [6][7][8] Various empirical solvent polarity parameters have been used to describe the influence of solvents on physicochemical solute properties. 9One particularly useful set consists of complementary Lewis acid-base solvent parameters, now known for most common organic solvents.10,11 It was found for example, by analysis of the variation of Kamlet-Taft's, β and α values, 12 for mixtures of methanol and other organic solvents, that one important factor influencing the basicity or acidity of solvent mixtures is due to an order/disorder process, particularly in binary mixtures of protic solvents with non-hydrogen bond donor (non-HBD) solvents. 12,13 Nucleotides play a key role in almost all kinds of metabolic processes. Much effort was devoted to the complexes of AMP, adenosine 5′-monophosphate, with metal ions. The properties and structures of binary complexes of most metal ion-AMP systems in aqueous solution are now relatively well described.14,15 Depending on the kind of metal ion involved, coordination occurs not only to the phosphate chain but also to N-1, leading thus to macrochelates.Thallium has been recognized as a toxic element for many years. It produces a variety of adverse effects in human beings. This element acts on the central nervous system and induces an inflammatory response. 16,17 However, the metabolic action and mechanism and fate of thallium toxicity are still not well understood, though there is some experimental evidence that suggests sulfur-containing compounds have been the main detoxifying drug in the case of poisoning. 17,18 Since thallium(I) shows marked similarities to that of potassium cation, 19 its interaction with nucleotides, the monomeric units of DNA and RNA, would be of major biochemical interest.This work deals with the study of thallium(I) complexes by AMP and the determination their stability constants in different solutions of methanol + water to show how the solvent and their mixtures with various dielectric constants affect the complexation.Recently, more attention has been paid to binary solvent mixtures in this field. 20-22 Solute-solvent interactions are much more complex in mixed solvent systems than in pure solvents, due to the possibility of preferential solvation by any of the solvents present in the mixtures. Moreover, the solvent-solvent interactions produced in solvent mixtures can affect the solutesolvent interactions and therefore they can also affect preferential solvations. 23At present, there are two more imp...

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Section: Introductionmentioning

confidence: 99%

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confidence: 99%

Complexation of Thallium(I) with Adenosine 5′-Monophosphate in Aqueous Methanol Solutions

2005

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“…4 These parameters mainly represent the properties of solvents as the electron acceptor, and it is known that they correlate with Mayer's acceptor number (AN). 5 The AN value is defined as the relative chemical shift of 31 P NMR of trimethylphosphine oxide in a solvent, and is widely used as a measure of the accepting property of the solvent molecule when combined with the Gutmann's donor number (DN), 6,7 which is a measure of the donating property. The β and α values of Kamlet-Taft are also proposed as the parameters to measure the solvent-solute interaction, which is related to the donating property.…”

Section: Introductionmentioning

confidence: 99%

“…Although the DN value of FA (24) is slightly smaller than that of DMF (26.6), such a comparison must be carefully done because the value of FA is estimated by a different method from that used for DMF. 6,7,12 Similarly to the case of FA, although the chemical characteristics of metal ions in TMU such as the solvation structure are compared with those in the other amides on the basis of DN values, [14][15][16] it should be noted that they are not determined by the same experimental method. It has been reported that the solvation number of the metal ion is variable from 4 to 6 according to the ionic size and charge in TMU with the bulky molecular structure.…”

Section: Introductionmentioning

confidence: 99%

Reevaluation of Donor Number Using Titration Calorimetry

et al. 2012

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“…In previous work from these laboratories (14) it was found that the combination of nitromethane, a weak donor solvent (15), and metal salts of the very weakly coordinating SbF6-anion promotes high denticity in Sn(I1)-and Pb(I1)-poly-(tertiaryphosphine) complexes. By analogy, in the present work we have used Hg(SbF6), (16) as the acceptor and MeN02 (or, in a few cases, MeN02--Me'CO) as solvent.…”

Section: Introductionmentioning

confidence: 99%

A multinuclear (¹H, ³¹P, ¹⁹⁹Hg) nuclear magnetic resonance study of some complexes of mercury(II) with ditertiary phosphines

Dean¹,

Srivastava²

1985

Can. J. Chem.

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From Hg(SbF6), and an appropriate amount of the ligands Ph2PCHRPPh2 (R = H or Me), 2 : 2, 1 : 2, and 1 : 3 M : L complexes have been prepared in MeN02 solution and characterized by 'H, 3'P, and "Hg nmr spectroscopy. The 2: 2 complexes are ligand-bridged, as are [Hg(Ph2PCH2PPh2)(Ph?PCHMePPh2)Hg]4' and [Hg(Ph2~CH2PPh2)2~g]3' (prepared from Hg(SbF6)2, Ag(AsF6), or Ag(SbF6) and the ligand), examined by nmr for comparison. The complex [Hg(pPhZPCHMePPh2)ZHg]4+ exists as two isomers, which interconvert slowly on the preparative timescale. The 1 :2 complexes, and the analogous mixed ligand complex are shown by their nmr spectral properties to be examples of tetrahedral bis(che1ate) complexes, which are very unusual for the Ph2PCHRPPh2 ligands. In the 1 :3 complexes, and the one of the two possible mixed complexes identified, both q l -and q2-ligands appear to be present and these undergo rapid intramolecular ql-to-q' exchange. The q '-bonding mode of Ph2PCH2PPh2 also occurs in [(q2-Ph2P(CH2)2PPh2)Hg(q'-Ph2PCHzPPh2)2]2' and [Hg(ql-Ph2PCH2PPh2),I3, as evidenced by their reduced temperature 3'P nmr spectra in Me2CO-MeN02.The complex [ H~(~' -P~~P C H~P P~~)~]~' has "P and ""Hg nmr spectral properties significantly different from those of its acyclic analog [Hg(PMePh2),IZ'. To place this anomaly in perspective, the "P and "' Hg nmr spectra of a much wider series of new bis (che1ate) From thedata for the last two series, it is found that only the bis(che1ate) complex of Ph2PCH2PPh2 shows a large anomaly in its Iy'Hg chemical shift (anomalously high shielding), and that in' J ( H~P ) , and "P chemical shifts vary systematically with the ligand combination; of particular note, 'J (HgP) to LL decreases as the chelate ring size of L'L' increases. These observations are discussed in terms of the variation in the intra-and inter-chelate PHgP angles expected in the complexes. A partir des donnkes se rapportant aux deux dernikres sCries, on a trouvC que le complexe bis(chClat6) de Ph2PCH2PPh2 est le seul a presenter une grande anomalie dans son dkplacement chimique du "' Hg (blindage anormalement grand); par ailleurs, on a Ctabli que, dans le complexe de [H~(LL)(L'L')]~', les valeurs de 2J(PP), de 'J(HgP) ainsi que les dCplacements chimiques du 31P varient d'une f a~o n systimatique avec la combinaison de ligand alors qu'il faut particulierement noter que la valeur de 'J de HgP i LL diminue lorsque la taille du cycle du chelate L'L' augmente. On discute de ces observations en fonction de la variation que I'on peut prkvoir pour les angles PHgP internes et entre les chelates dans les complexes.[Traduit par le journal]

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Coordination reactions in non aqueous solutions - The role of the donor strength

Cited by 390 publications

References 2 publications

Complexation of Thallium(I) with Adenosine 5′-Monophosphate in Aqueous Methanol Solutions

Complexation of Thallium(I) with Adenosine 5′-Monophosphate in Aqueous Methanol Solutions

Reevaluation of Donor Number Using Titration Calorimetry

A multinuclear (¹H, ³¹P, ¹⁹⁹Hg) nuclear magnetic resonance study of some complexes of mercury(II) with ditertiary phosphines

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Coordination reactions in non aqueous solutions - The role of the donor strength

Cited by 390 publications

References 2 publications

Complexation of Thallium(I) with Adenosine 5′-Monophosphate in Aqueous Methanol Solutions

Complexation of Thallium(I) with Adenosine 5′-Monophosphate in Aqueous Methanol Solutions

Reevaluation of Donor Number Using Titration Calorimetry

A multinuclear (1H, 31P, 199Hg) nuclear magnetic resonance study of some complexes of mercury(II) with ditertiary phosphines

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A multinuclear (¹H, ³¹P, ¹⁹⁹Hg) nuclear magnetic resonance study of some complexes of mercury(II) with ditertiary phosphines