Coordination modes in the formation of the ternary Am(III), Cm(III), and Eu(III) complexes with EDTA and NTA: TRLFS, 13C NMR, EXAFS, and thermodynamics of the complexation

The formation and the structure of the ternary complexes of trivalent Am, Cm, and Eu with mixtures of EDTA+NTA (ethylenediamine tetraacetate and nitrilotriacetate) have been studied by time-resolved laser fluorescence spectroscopy, 13C NMR, extended X-ray absorption fine structure, and two-phase metal ion equilibrium distribution at 6.60 m (NaClO4) and a hydrogen ion concentration value (pcH) between 3.60 and 11.50. In the ternary complexes, EDTA binds via four carboxylates and two nitrogens, while the binding of the NTA varies with the hydrogen ion concentration, pcH, and the concentration ratios of the metal ion and the ligand. When the concentration ratios of the metal to ligand is low (1:1:1-1:1:2), two ternary complexes, M(EDTA)(NTAH)(3-) and M(EDTA)(NTA)(4-), are formed at pcH ca. 9.00 in which NTA binds via three carboxylates, via two carboxylates and one nitrogen, or via two carboxylates and a H2O. At higher ratios (1:1:20 and 1:10:10) and pcH's of ca. 9.00 and 11.50, one ternary complex, M(EDTA)(NTA)(4-), is formed in which NTA binds via three carboxylates and not via nitrogen. The two-phase equilibrium distribution studies at tracer concentrations of Am, Cm, and Eu have also confirmed the formation of the ternary complex M(EDTA)(NTA)(4-) at temperatures between 0 and 60 degrees C. The stability constants (log beta111) for these metal ions increase with increasing temperature. The endothermic enthalpy and positive entropy indicated a significant effect of cation dehydration in the formation of the ternary complexes at high ionic strength.     

Studies of Size-Based Selectivity in Aqueous Ternary Complexes of Americium(III) or Lanthanide(III) Cations

Spectrophotometric and calorimetric titrations were used to determine the equilibrium constants (log₁₀ K ₁₁₁) and enthalpies of formation (ΔH ₁₁₁) for aqueous ternary complexes of the form M(L^a)(L^b) (M = Nd³⁺, Sm³⁺, Tb³⁺, Ho³⁺, Er³⁺, or Am³⁺; L^a = DTPA^5?, DO3A^3?, or CDTA^4?; L^b = oxalate (Ox), malonate (Mal), or iminodiacetate (IDA)). Inner-sphere ternary complexes were readily formed with the septadentate DO3A (1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid) and hexadentate CDTA (trans-1,2-diaminocyclohexanetetraacetic acid) ligands, whose binary complexes have residual metal-coordinated water molecules that are readily displaced by the smaller secondary ligands. The stability constants for the formation of lanthanide–CDTA complexes with Ox, Mal, and IDA generally increase with decreasing ionic radius when steric hindrance is minimal, with the trend in the M(CDTA)^? formation constants overshadowing any size-based reversal in the stepwise ternary complexation constants. Similar ternary complexes with DO3A showed little increase in thermodynamic stability compared to analogous CDTA complexes and no preference for larger Ln cations. The octadentate DTPA (diethylenetriaminepentaacetic acid) ligand proved too large to form ternary complexes to a measurable extent with any of the secondary ligands investigated, despite the presence of one residual inner sphere water molecule.     

Thermodynamic study on the complexation of Am(III) and Eu(III) with tetradentate nitrogen ligands: a probe of complex species and reactions in aqueous solution

A thermodynamic investigation has been performed to study the complexation of trivalent metal (M) ions (M = Am(III), Eu(III)) with tetradentate ligands (L), 6,6'-bis(5,6-dialkyl-1,2,4-triazin-3-yl)-2,2'-bipyridines (BTBPs), by using relativistic quantum mechanical calculations. The structures and stabilities of the inner-sphere BTBPs complexes were explored in the presence of various counterions such as NO(3)(-), Cl(-), and ClO(4)(-). According to our calculations, Am(III) and Eu(III) can chelate eight or nine water molecules at most, whereas more stable species like M(NO(3))(3)(H(2)O)(4) tend to be formed in the presence of nitrate ions. The inner sphere of the BTBPs complexes can accommodate four water molecules or three nitrate ions based on our calculations, forming species such as [ML(H(2)O)(4)](3+) and ML(NO(3))(3). Compared with Eu(III) complexes, the Am(III) counterparts have obviously lower binding energies in both the gas phase and solution. In addition, the solvent effect significantly decreases the binding energies of the BTBPs complexes. It has been found that the complexing reactions, in which products and reactants possess the same or close number of nitrate ions, are more favorable for formation of the BTBPs complexes. In short, the reactions of M(NO(3))(3)(H(2)O)(4) → ML(NO(3))(3) and [M(NO(3))(H(2)O)(7)](2+) → [ML(2)(NO(3))](2+) are probably the dominant ones in the Am(III)/Eu(III) separation process.     

Lanthanide(III) and group 13 metal ion complexes of tripodal amino phosphinate ligands

The tripodal amino-phosphinate ligands, tris(4-(phenylphosphinato)-3-benzyl-3-azabutyl)amine (H(3)ppba.2HCl.H(2)O) and tris(4-(phenylphosphinato)-3-azabutyl)amine (H(3)ppa.HCl.H(2)O) were synthesized and reacted with Al(3+), Ga(3+), In(3+) and the lanthanides (Ln(3+)). At 2 : 1 H(3)ppba to metal ratios, complexes of the type [M(H(3)ppba)(2)](3+)(M = Al(3+), Ga(3+), In(3+), Ho(3+)-Lu(3+)) were isolated. The bicapped [Ga(H(3)ppba)(2)](NO(3))(2)Cl.3CH(3)OH was structurally characterized and was shown indirectly by various techniques to be isostructural with the other [M(H(3)ppba)(2)](3+) complexes. Also, at 2 : 1 H(3)ppba to metal ratios, complexes of the type [M(H(4)ppba)(2)](5+)(M = La(3+)-Tb(3+)) were characterized, and the X-ray structure of [Gd(H(4)ppba)(2)](NO(3))(4)Cl.3CH(3)OH was determined. At 1 : 1 H(3)ppba to metal ratios, complexes of the type [M(H(4)ppba)](4+)(M = La(3+)-Er(3+)) were isolated and characterized. Elemental analysis and spectroscopic evidence supported the formation of a 1 : 1 monocapped complex. Reaction of 1 : 1 ratios of H(3)ppa with Ln(3+) and In(3+) yielded complexes of the type [M(H(3)ppa)](3+)(M = La(3+)-Yb(3+)) but with Ga(3+), complex of the type [Ga(ppa)].3H(2)O was obtained. Reaction of 1 : 1 ratios of H(3)ppa with Ln(3+) and In(3+) yielded complexes of the type [M(H(3)ppa)](3+)(M = La(3+)-Yb(3+)) but with Ga(3+) a neutral complex [Ga(ppa)].3H(2)O was obtained. The formation of an encapsulated 1 : 1 complex is supported by elemental analysis and spectroscopic evidence.     

Ternary complexes of the Cu(II) and Ni(II) chelates of edta and dcta with cyanide and ethylenediamine

The formation of the ternary complexes CuEDTA(en)(2-), CuEDTA(CN)(3-), CuDCTA(CN)(3-), NiDCTA(CN)(3-) and NiEDTA(en)(2-) has been established spectrophotometrically. The stability constants found were log K = 2.87 +/- 0.03, 3.76 +/- 0.06, 2.64 +/- 0.35, 2.41 +/- 0.21 and 2.74 +/- 0.35 respectively. For the system CuDCTA(2-) + en no ternary complex was observed, instead Cu(en)(2)(2+) was formed. No reaction was found for the systems CoEDTA(2-) + N(3)(-), CoDCTA(2-) + N(3)(-), NiDCTA(2-) + en, NiDCTA(2-) + phen, NiEDTA(2-) + phen, NiDCTA(2-) + N(3)(-), NiEDTA(2-) + N(3)(-), CrEDTA(-) + NH(3), CrEDTA(-) + CN(-), CuEDTA(2-) + N(3) and CuEDTA(2-) + N(3)(-). The systems CoEDTA(2-) + en and CoDCTA(2-) + en involve more than one equilibrium. The absorption spectra of the ternary complexes between 500 and 850 nm are reported.     

Nitrile hydration by thiolate- and alkoxide-ligated Co-NHase analogues. Isolation of Co(III)-amidate and Co(III)-iminol intermediates

Nitrile hydratases (NHases) are thiolate-ligated Fe(III)- or Co(III)-containing enzymes, which convert nitriles to the corresponding amide under mild conditions. Proposed NHase mechanisms involve M(III)-NCR, M(III)-OH, M(III)-iminol, and M(III)-amide intermediates. There have been no reported crystallographically characterized examples of these key intermediates. Spectroscopic and kinetic data support the involvement of a M(III)-NCR intermediate. A H-bonding network facilitates this enzymatic reaction. Herein we describe two biomimetic Co(III)-NHase analogues that hydrate MeCN, and four crystallographically characterized NHase intermediate analogues, [Co(III)(S(Me2)N(4)(tren))(MeCN)](2+) (1), [Co(III)(S(Me2)N(4)(tren))(OH)](+) (3), [Co(III)(S(Me2)N(4)(tren))(NHC(O)CH(3))](+) (2), and [Co(III)(O(Me2)N(4)(tren))(NHC(OH)CH(3))](2+) (5). Iminol-bound 5 represents the first example of a Co(III)-iminol compound in any ligand environment. Kinetic parameters (k(1)(298 K) = 2.98(5) M(-1) s(-1), ΔH(?) = 12.65(3) kcal/mol, ΔS(?) = -14(7) e.u.) for nitrile hydration by 1 are reported, and the activation energy E(a) = 13.2 kcal/mol is compared with that (E(a) = 5.5 kcal/mol) of the NHase enzyme. A mechanism involving initial exchange of the bound MeCN for OH- is ruled out by the fact that nitrile exchange from 1 (k(ex)(300 K) = 7.3(1) × 10(-3) s(-1)) is 2 orders of magnitude slower than nitrile hydration, and that hydroxide bound 3 does not promote nitrile hydration. Reactivity of an analogue that incorporates an alkoxide as a mimic of the highly conserved NHase serine residue shows that this moiety facilitates nitrile hydration under milder conditions. Hydrogen-bonding to the alkoxide stabilizes a Co(III)-iminol intermediate. Comparison of the thiolate versus alkoxide intermediate structures shows that C≡N bond activation and C═O bond formation proceed further along the reaction coordinate when a thiolate is incorporated into the coordination sphere.     

Structural characterization and formation kinetics of sitting-atop (SAT) complexes of some porphyrins with copper(II) ion in aqueous acetonitrile relevant to porphyrin metalation mechanism. Structures of aquacopper(II) and cu(II)-SAT complexes as determined by XAFS spectroscopy

The formation of the sitting-atop (SAT) complexes of 5,10,15,20-tetraphenylporphyrin (H(2)tpp), 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin (H(2)t(4-Clp)p), 5,10,15,20-tetramesitylporphyrin (H(2)tmp), and 2,3,7,8,12,13,17,18-octaethylporphyrin (H(2)oep) with the Cu(II) ion was spectrophotometrically confirmed in aqueous acetonitrile (AN), and the formation rates were determined as a function of the water concentration (C(W)). The decrease in the conditional first-order rate constants with the increasing C(W) was reproduced by taking into consideration the contribution of [Cu(H(2)O)(an)(5)](2+) in addition to [Cu(an)(6)](2+) to form the Cu(II)-SAT complexes. The second-order rate constants for the reaction of [Cu(an)(6)](2+) and [Cu(H(2)O)(an)(5)](2+) at 298 K were respectively determined as follows: (4.1 +/- 0.2) x 10(5) and (3.6 +/- 0.2) x 10(4) M(-1) s(-1) for H(2)tpp, (1.15 +/- 0.06) x 10(5) M(-1) s(-1) and negligible for H(2)t(4-Clp)p, and (4.8 +/- 0.3) x 10(3) and (1.3 +/- 0.3) x 10(2) M(-1) s(-1) for H(2)tmp. Since the reaction of H(2)oep was too fast to observe the reaction trace due to the dead time of 2 ms for the present stopped-flow technique, the rate constant was estimated to be greater than 1.5 x 10(6) M(-1) s(-1). According to the structure of the Cu(II)-SAT complexes determined by the fluorescent XAFS measurements, two pyrrolenine nitrogens of the meso-substituted porphyrins (H(2)tpp and H(2)tmp) bind to the Cu(II) ion with a Cu-N(pyr) distance of ca. 2.04 A, while those of the beta-pyrrole-substituted porphyrin (H(2)oep) coordinate with the corresponding bond distance of 1.97 A. The shorter distance of H(2)oep is ascribed to the flexibility of the porphyrin ring, and the much greater rate for the formation of the Cu(II)-SAT complex of H(2)oep than those for the meso-substituted porphyrins is interpreted as due to a small energetic loss at the porphyrin deformation step during the formation of the Cu(II)-SAT complex. The overall formation constants, beta(n), of [Cu(H(2)O)(n)()(an)(6)(-)(n)](2+) for the water addition in aqueous AN were spectrophotometrically determined at 298 K as follows: log(beta(1)/M(-1)) = 1.19 +/- 0.18, log(beta(2)/M(-2)) = 1.86 +/- 0.35, and log(beta(3)/M(-3)) = 2.12 +/- 0.57. The structure parameters around the Cu(II) ion in [Cu(H(2)O)(n)(an)(6-n)](2+) were determined using XAFS spectroscopy.     

Stabilities and isomeric equilibria in aqueous solution of monomeric metal ion complexes of adenosine 5'-diphosphate (ADP3-) in comparison with those of adenosine 5'-monophosphate (AMP2-)

Under experimental conditions in which the self-association of the adenine phosphates (AP), that is, of adenosine 5'-monophosphate (AMP(2-)) and adenosine 5'-diphosphate (ADP(3-)), is negligible, potentiometric pH titrations were carried out to determine the stabilities of the M(H;AP) and M(AP) complexes where M(2+)=Mg(2+), Ca(2+), Sr(2+), Ba(2+), Mn(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), or Cd(2+) (25 degrees C; I=0.1 M, NaNO(3)). It is concluded that in the M(H;AMP)(+) species M(2+) is bound at the adenine moiety and in the M(H;ADP) complexes at the diphosphate unit; however, the proton resides in both types of monoprotonated complexes at the phosphate residue. The stabilities of nearly all the M(AMP) and M(ADP)(-) complexes are significantly larger than what is expected for a sole coordination of M(2+) to the phosphate residue. This increased complex stability is attributed, in agreement with previous (1)H NMR shift studies and further information existing in the literature, to the formation of macrochelates of the phosphate-coordinated metal ions with N7 of the adenine residues. On the basis of recent measurements with simple phosphate monoesters and phosphonate ligands (R-MP(2-)) as well as with diphosphate monoesters (R-DP(3-)), where R is a noncoordinating and noninhibiting residue, the increased stabilities of the M(AMP) and M(ADP)(-) complexes due to the M(2+)-N7 interaction could be evaluated and the extent of macrochelate formation calculated. The results show that the formation degrees of the macrochelates for the complexes of the alkaline earth ions are small (about 15 % at the most), whereas for the 3d metal ions as well as for Zn(2+) and Cd(2+) the formation degrees vary between about 15 % (Mn(2+)) and 75 % (Ni(2+)) with values of about 40 and 50 % for Zn(2+) and Cu(2+), respectively. It is interesting to note, taking earlier results for M(ATP)(2-) complexes also into account (ATP(4-)=adenosine 5'-triphosphate), that for a given metal ion in nearly all instances the formation degrees of the macrochelates are within the error limits the same for M(AMP), M(ADP)(-) and M(ATP)(2-) complexes; except for Co(2+) and Ni(2+) it holds M(AMP) > M(ADP)(-) approximately M(ATP)(2-). This result is astonishing if one considers that the absolute stability constants of these complexes, which are determined largely by the affinity of the phosphate residues, can differ by more than two orders of magnitude. The impact and conclusions of these observations for biological systems are shortly lined out.     

Lanthanide(III) complexes of novel mixed carboxylic-phosphorus acid derivatives of diethylenetriamine: a step towards more efficient MRI contrast agents

Three novel phosphorus-containing analogues of H(5)DTPA (DTPA = diethylenetriaminepentaacetate) were synthesised (H6L1, H5L2, H5L3). These compounds have a -CH2-P(O)(OH)-R function (R = OH, Ph, CH2NBn2) attached to the central nitrogen atom of the diethylenetriamine backbone. An NMR study reveals that these ligands bind to lanthanide(III) ions in an octadentate fashion through the three nitrogen atoms, a P-O oxygen atom and four carboxylate oxygen atoms. The complexed ligand occurs in several enantiomeric forms due to the chirality of the central nitrogen atom and the phosphorus atom upon coordination. All lanthanide complexes studied have one coordinated water molecule. The residence times (tau(M)298) of the coordinated water molecules in the gadolinium(III) complexes of H6L1 and H5L2 are 88 and 92 ns, respectively, which are close to the optimum. This is particularly important upon covalent and noncovalent attachment of these Gd(3+) chelates to polymers. The relaxivity of the complexes studied is further enhanced by the presence of at least two water molecules in the second coordination sphere of the Gd(3+) ion, which are probably bound to the phosphonate/phosphinate moiety by hydrogen bonds. The complex [Gd(L3)(H2O)](2-) shows strong binding ability to HSA, and the adduct has a relaxivity comparable to MS-325 (40 s(-1) mM(-1) at 40 MHz, 37 degrees C) even though it has a less favourable tau(M) value (685 ns). Transmetallation experiments with Zn(2+) indicate that the complexes have a kinetic stability that is comparable to-or better than-those of [Gd(dtpa)(H2O)](2-) and [Gd(dtpa-bma)(H2O)].     

Nitrous acid as a source of NO and NO(2) in the reaction with a macrocyclic superoxorhodium(III) complex

The title reaction takes place according to the stoichiometry 2L(2)RhOO(2+) + 3HNO(2) + H(2)O --> 2L(2)Rh(OH(2))(3+) + 3NO(3)(-) + H(+) (L(2) = meso-Me(6)-[14]ane-N(4)). The kinetics are second order in HNO(2) and independent of the concentration of L(2)RhOO(2+), rate = (k(1) + k(2)[H(+)])[HNO(2)](2), where k(1) = 10.9 M(-1) s(-1) and k(2) = 175 M(-2) s(-1) at 25 degrees C and 0.10 M ionic strength. The reaction produces two observable intermediates, the nitrato (L(2)RhONO(2)(2+)) and hydroperoxo (L(2)RhOOH(2+)) complexes. The product analysis and kinetics are indicative of the initial rate-controlling formation of NO and NO(2), both of which react rapidly with L(2)RhOO(2+) in subsequent steps. The reaction with NO produces mainly L(2)RhONO(2)(2+), which hydrolyzes to L(2)Rh(OH(2))(3+) and NO(3)(-). Another minor pathway generates the hydroperoxo complex, which was detected by its known reaction with Fe(aq)(2+). The reaction of NO(2) with L(2)RhOO(2+) requires an additional equivalent of HNO(2) and produces L(2)Rh(OH(2))(3+) and NO(3)(-) via a proposed peroxynitrato complex L(2)RhOONO(2)(2+). This work provides strong evidence for the long-debated reaction between HNO(2) and H(2)NO(2)(+) to generate N(2)O(3).     

Metal complexes of tetrapodal ligands: synthesis, spectroscopic and thermal studies, and X-ray crystal structure studies of Na(I), Ca(II), Sr(II), and Ba(II) complexes of tetrapodal ligands N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine and N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine

Twelve complexes 1-12 of general category [M(ligand)(anion)(x)(water)(y)], where ligand = N,N,N',N'-tetrakis(2-hydroxypropyl/ethyl)ethylenediamine (HPEN/HEEN), anion = anions of picric acid (PIC), 3,5-dinitrobenzoic acid (DNB), 2,4-dinitrophenol (DNP), and o-nitrobenzoic acid (ONB), M = Ca(2+), Sr(2+), Ba(2+), or Na(+), x = 1 and 2, and y = 0-4, were synthesized. All of these complexes were characterized by elemental analysis, IR, (1)H and (13)C NMR, and thermal studies. X-ray crystal studies of these complexes 1-12, [Ca(HPEN)(H(2)O)(2)](PIC)(2).H(2)O (1), [Ca(HEEN)(PIC)](PIC) (2), Ba(HPEN)(PIC)(2) (3), [Na(HPEN)(PIC)](2) (4), Ca(HPEN)(H(2)O)(2)](DNB)(2).H(2)O (5),Ca(HEEN)(H(2)O)](DNB)(2).H(2)O (6), [Sr(HPEN)(H(2)O)(3)](DNB)(2) (7), [Ba(HPEN)(H(2)O)(2)](DNB)(2).H(2)O](2) (8), [[Ba(HEEN)(H(2)O)(2)](ONB)(2)](2) (9), [[Sr(HPEN)(H(2)O)(2)](DNP)(2)](2) (10), [[Ba(HPEN)(H(2)O)(2)](DNP)(2)](2) (11), and [Ca(HEEN)(DNP)](DNP) (H(2)O) (12), have been carried out at room temperature. Factors which influence the stability and the type of complex formed have been recognized as H-bonding interactions, presence/absence of solvent, nature of the anion, and nature of the cation. Both the ligands coordinate the metal ion through all the six available donor atoms. The complexes 1 and 5-11 have water molecules in the coordination sphere, and their crystal structures show that water is playing a dual character. It coordinates to the metal ion on one hand and strongly hydrogen bonds to the anion on the other. These strong hydrogen bonds stabilize the anion and decrease the cation-anion interactions by many times to an extent that the anions are completely excluded out of the coordination sphere and produce totally charge-separated complexes. In the absence of water molecules as in 2 and 3 the number of hydrogen bonds is reduced considerably. In both the complexes the anions case interact more strongly with the metal ion to give rise to a partially charge-separated 2 or tightly ion-paired 3 complex. High charge density Ca(2+) forms only monomeric complexes. It has more affinity toward stronger nucleophiles such as DNP and PIC with which it gives partially charge-separated eight-coordinated complexes. But with relatively weaker nucleophile like DNB, water replaces the anion and produces a seven coordinated totally charge-separated complex. Sr(2+) with lesser charge/radius ratio forms only charge-separated monomeric as well as dimeric complexes. Higher coordination number of Sr(2+) is achieved with coordinated water molecules which may be bridging or nonbridging in nature. All charge-separated complexes of the largest Ba(2+) are dimeric with bridging water molecules. Only one monomeric ion-paired complex was obtained with Ba(PIC)(2). Na(+) forms a unique dinuclear cryptand-like complex with HPEN behaving as a heptadentate chelating-cum-bridging ligand.     

Effect of Pyridyl Donors in the Chelation of Aluminum(III), Gallium(III), and Indium(III)

A new preparation of N,N'-bis(2-pyridylmethyl)ethylenediamine-N,N'-diacetic acid (H(2)bped) is reported, and its properties of complexation with Al(III), Ga(III), In(III), and Co(III) are investigated. The molecular structure of the cobalt(III) complex [Co(bped)]PF(6).CH(3)CN.H(2)O (C(20)H(25)CoF(6)N(5)O(5)P) has been solved by X-ray methods; the complex crystallizes in the triclinic space group P&onemacr;, with a = 10.611(2) ?, b = 12.720(2) ?, c = 9.868(1) ?, alpha = 102.70(1) degrees, beta =93.60(1) degrees, gamma = 106.96(1) degrees, and Z = 2. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.041 (R(w) = 0.038) for 4312 reflections with I > 3sigma(I). The Co(III) ion is coordinated in a distorted octahedral geometry with an N(4)O(2) donor atom set. The carboxylato oxygen atoms are coordinated trans, while the pyridyl nitrogen atoms are coordinated cis. The largest distortion from octahedral geometry is the N(pyridyl)-Co-N(pyridyl) angle of 107 degrees. Complex formation constants have been measured at 25 degrees C (&mgr; = 0.16 M (NaCl)). log K([M(bped)](+)) (log K([M(bped)(OH)])): M = Al, 10.85 (6.37); M = Ga, 19.89 (15.62); M = In, 22.6 (15.44). A protonated complex was also detected, [Ga(Hbped)](2+), log K = 21.79. The order of stability is In(III) > Ga(III) > Al(III) for the binary species, [M(bped)](+). The solution structures of the complexes have been probed in multinuclear NMR ((1)H, (13)C, (27)Al) studies, and these solution structures are compared with the solid state structure of the cobalt(III) complex. The complexes [In(bped)](+) and [In(bped)(OH)] are proposed to contain 7-coordinate In(III) with water and hydroxide completing the respective coordination spheres. The gallium complexes are proposed to be 6-coordinate: the [Ga(Hbped)](2+) complex contains a nondeprotonated carboxylic acid group which is not coordinated, and [Ga(bped)(OH)] contains a coordinated hydroxide which displaces a carboxylato donor. The [Al(bped)(OH)] complex may be 5-coordinate on the basis of its downfield (27)Al NMR chemical shift, 54 ppm.     

Thermodynamics, kinetics, and mechanism of the stepwise dissociation and formation of Tris(L-lysinehydroxamato)iron(III) in aqueous acid

pK(a) values for the hydroxamic acid, alpha-NH(3)(+), and epsilon-NH(3)(+) groups of L-lysinehydroxamic acid (LyHA, H(3)L(2+)) were found to be 6.87, 8.89, and 10.76, respectively, in aqueous solution (I = 0.1 M, NaClO(4)) at 25 degrees C. O,O coordination to Fe(III) by LyHA is supported by H(+) stoichiometry, UV-vis spectral shifts, and a shift in nu(CO) from 1648 to 1592 cm(-1) upon formation of mono(L-lysinehydroxamato)tetra(aquo)iron(III) (Fe(H(2)L)(H(2)O)(4)(4+)). The stepwise formation of tris(L-lysinehydroxamato)iron(III) from Fe(H(2)O)(6)(3+) and H(3)L(2+) was characterized by spectrophotometric titration, and the values for log beta(1), log beta(2), and log beta(3) are 6.80(9), 12.4(2), and 16.1(2), respectively, at 25 degrees C and I = 2.0 M (NaClO(4)). Stopped-flow spectrophotometry was used to study the proton-driven stepwise ligand dissociation kinetics of tris(L-lysinehydroxamato)iron(III) at 25 degrees C and I = 2.0 M (HClO(4)/NaClO(4)). Defining k(n) and k(-n) as the stepwise ligand dissociation and association rate constants and n as the number of bound LyHA ligands, k(3), k(-3), k(2), k(-2), k(1), and k(-1) are 3.0 x 10(4), 2.4 x 10(1), 3.9 x 10(2), 1.9 x 10(1), 1.4 x 10(-1), and 1.2 x 10(-1) M(-1) s(-1), respectively. These rate and equilibrium constants are compared with corresponding constants for Fe(III) complexes of acetohydroxamic acid (AHA) and N-methylacetohydroxamic acid (NMAHA) in the form of a linear free energy relationship. The role of electrostatics in these complexation reactions to form the highly charged Fe(LyHA)(3)(6+) species is discussed, and an interchange mechanism mediated by charge repulsion is presented. The reduction potential for tris(L-lysinehydroxamato)iron(III) is -214 mV (vs. NHE), and a comparison to other hydroxamic acid complexes of Fe(III) is made through a correlation between E(1/2) and pFe.     

Acid-base and metal ion binding properties of guanylyl(3'-->5')guanosine (GpG-) and 2'-deoxyguanylyl(3'-->5')-2'-deoxyguanosine [d(GpG)-] in aqueous solution

The acidity constants of guanylyl(3'-->5')guanosine (GpG(-)) and 2'-deoxyguanylyl(3'-->5')-2'-deoxyguanosine [d(GpG)(-)] for the deprotonation of their (N1)H sites were measured by potentiometric pH titrations in aqueous solution (25 degrees C; I = 0.1 M, NaNO(3)). The same method was used for the determination of the stability constants of the 1:1 complexes formed between Mg(2+), Ni(2+), or Cd(2+) (= M(2+)) and (GG-H)(2-), and in the case of Mg(2+) also of (GG-2H)(3-), where GG(-) = GpG(-) or d(GpG)(-). The stability constants of the M(GG)(+) complexes were estimated. The acidity constants of the H(dGuo)(+) and dGuo species (dGuo = 2'-deoxyguanosine) and the stability constants of the corresponding M(dGuo)(2+) and M(dGuo-H)(+) complexes were also measured. Comparison of these and related data allows the conclusion that N7 of the 5'G unit in GG(-) is somewhat more basic than the one in the 3'G moiety; the same holds for the (N1)(-) sites. On the basis of comparisons with the stability constants measured for the dGuo complexes, it is concluded that M(2+) binding of the GG dinucleoside monophosphates occurs predominantly in a mono-site fashion, meaning that macrochelate formation is not very pronounced. Indeed, it was a surprise to find that the stabilities of the complexes of dGuo or (dGuo-H)(-) and the corresponding ones derived from GG(-) are so similar. Consequently, it is suggested that in the M(GG)(+) and M(GG-H) complexes the metal ion is mainly located at N7 of the 5'G unit since this is the more basic site allowing also an outer-sphere interaction with the C6 carbonyl oxygen and because this coordination mode is also favorable for an electrostatic interaction with the negatively charged phosphodiester bridge. It is further suggested that Mg(2+) binding (which is rather weak compared to that of Ni(2+) and Cd(2+)) occurs mainly in an outer-sphere mode, and on the basis of the so-called Stability Ruler it is concluded that the binding properties of Zn(2+) to the GG species are similar to those of Ni(2+) and Cd(2+).     

Comparison of the surprising metal-ion-binding properties of 5- and 6-uracilmethylphosphonate (5Umpa2- and 6Umpa2-) in aqueous solution and crystal structures of the dimethyl and di(isopropyl) esters of H2(6Umpa)

5- and 6-Uracilmethylphosphonate (5Umpa(2-) and 6Umpa(2-)) as acyclic nucleotide analogues are in the focus of anticancer and antiviral research. Connected metabolic reactions involve metal ions; therefore, we determined the stability constants of M(Umpa) complexes (M(2+)=Mg(2+), Ca(2+), Mn(2+), Co(2+), Cu(2+), Zn(2+), or Cd(2+)). However, the coordination chemistry of these Umpa species is also of interest in its own right, for example, the phosphonate-coordinated M(2+) interacts with (C4)O to form seven-membered chelates with 5Umpa(2-), thus leading to intramolecular equilibria between open (op) and closed (cl) isomers. No such interaction occurs with 6Umpa(2-). In both M(Umpa) series deprotonation of the uracil residue leads to the formation of M(Umpa-H)(-) complexes at higher pH values. Their stability was evaluated by taking into account the fact that the uracilate residue can bind metal ions to give M(2)(Umpa-H)(+) species. This has led to two further important insights: 1) In M(6Umpa-H)-cl the H(+) is released from (N1)H, giving rise to six-membered chelates (degrees of formation of ca. 90 to 99.9 % with Mn(2+), Co(2+), Cu(2+), Zn(2+), or Cd(2+)). 2) In M(5Umpa-H)$-cl the (N3)H is deprotonated, leading to a higher stability of the seven-membered chelates involving (C4)O (even Mg(2+) and Ca(2+) chelates are formed up to approximately 50 %). In both instances the M(Umpa-H)-op species led to the formation of M(2)(Umpa-H)(+) complexes that have one M(2+) at the phosphonate and one at the (N3)(-) (plus carbonyl) site; this proves that nucleotides can bind metal ions independently at the phosphate and the nucleobase residues. X-ray structural analyses of 6Umpa derivatives show that in diesters the phosphonate group is turned away from the uracil residue, whereas in H(2)(6Umpa) the orientation is such that upon deprotonation in aqueous solution a strong hydrogen bond is formed between (N1)H and PO(3) (2-); replacement of the hydro gen with M(2+) gives the M(6Umpa-H)-cl chelates mentioned.     

Acetate-Bridged Platinum(III) Complexes Derived from Cisplatin

Oxidation of the acetate-bridged half-lantern platinum(II) complex cis-[Pt(II)(NH(3))(2)(μ-OAc)(2)Pt(II)(NH(3))(2)](NO(3))(2), [1](NO(3))(2), with iodobenzene dichloride or bromine generates the halide-capped platinum(III) species cis-[XPt(III)(NH(3))(2)(μ-OAc)(2)Pt(III)(NH(3))(2)X](NO(3))(2), where X is Cl in [2](NO(3))(2) or Br in [3](NO(3))(2), respectively. These three complexes, characterized structurally by X-ray crystallography, feature short (≈2.6 ?) Pt-Pt separations, consistent with formation of a formal metal-metal bond upon oxidation. Elongated axial Pt-X distances occur, reflecting the strong trans influence of the metal-metal bond. The three structures are compared to those of other known dinuclear platinum complexes. A combination of (1)H, (13)C, (14)N, and (195)Pt NMR spectroscopy was used to characterize [1](2+)-[3](2+) in solution. All resonances shift downfield upon oxidation of [1](2+) to [2](2+) and [3](2+). For the platinum(III) complexes, the (14)N and (195)Pt resonances exhibit decreased line widths by comparison to those of [1](2+). Density functional theory calculations suggest that the decrease in the (14)N line width arises from a diminished electric field gradient at the (14)N nuclei in the higher valent compounds. The oxidation of [1](NO(3))(2) with the alternative oxidizing agent bis(trifluoroacetoxy)iodobenzene affords the novel tetranuclear complex cis-[(O(2)CCF(3))Pt(III)(NH(3))(2)(μ-OAc)(2)Pt(III)(NH(3))(μ-NH(2))](2)(NO(3))(4), [4](NO(3))(4), also characterized structurally by X-ray crystallography. In solution, this complex exists as a mixture of species, the identities of which are proposed.     

Sulfur-bridged Co(III)Pt(II)Co(III) trinuclear complexes with mixed aliphatic and aromatic thiolate ligands: effect of nonbridging ligands on the homochiral linkage of cobalt(III) octahedrons by platinum(II)

The reaction of [Ni[Co(aet)(2)(pyt)](2)](2+) (aet = 2-aminoethanethiolate, pyt = 2-pyridinethiolate) with [PtCl(4)](2)(-) gave an S-bridged Co(III)Pt(II)Co(III) trinuclear complex composed of two [Co(aet)(2)(pyt)] units, [Pt[Co(aet)(2)(pyt)](2)](2+) ([1](2+)). When a 1:1 mixture of [Ni[Co(aet)(2)(pyt)](2)](2+) and [Ni[Co(aet)(2)(en)](2)](4+) was reacted with [PtCl(4)](2)(-), a mixed-type S-bridged Co(III)Pt(II)Co(III) complex composed of one [Co(aet)(2)(pyt)] and one [Co(aet)(2)(en)](+) units, [Pt[Co(aet)(2)(en)][Co(aet)(2)(pyt)]](3+) ([2](3+)), was produced, together with [1](2+) and [Pt[Co(aet)(2)(en)](2)](4+). The corresponding Co(III)Pt(II)Co(III) trinuclear complexes containing pymt (2-pyrimidinethiolate), [Pt[Co(aet)(2)(pymt)](2)](2+) ([3](2+)) and [Pt[Co(aet)(2)(en)][Co(aet)(2)(pymt)]](3+) ([4](3+)), were also obtained by similar reactions, using [Ni[Co(aet)(2)(pymt)](2)](2+) instead of [Ni[Co(aet)(2)(pyt)](2)](2+). While [Pt[Co(aet)(2)(en)](2)](4+) formed both the deltalambda (meso) and deltadelta/lambdalambda (racemic) forms in a ratio of ca. 1:1, the preferential formation of the deltadelta/lambdalambda form was observed for [1](2+) (ca. deltalambda:deltadelta/lambdalambda = 1:3) and [2](3+) (ca. delta(en)lambda(pyt)/lambda(en)delta(pyt):deltadelta/lambdalambda = 1:2). Furthermore, [3](2+) and [4](3+) predominantly formed the deltadelta/lambdalambda form. These results indicate that the homochiral selectivity for the S-bridged Co(III)Pt(II)Co(III) trinuclear complexes composed of two octahedral [Co(aet)(2)(L)](0 or +) units is enhanced in the order L = en < pyt < pymt. The isomers produced were separated and optically resolved, and the crystal structures of the meso-type deltalambda-[1]Cl(2).4H(2)O and the spontaneously resolved deltadelta-[4](ClO(4))(3).H(2)O were determined by X-ray analyses. In deltalambda-[1](2+), the delta and Lambda configurational mer(S).trans(N(aet))-[Co(aet)(2)(pyt)] units are linked by a square-planar Pt(II) ion through four aet S atoms to form a linear-type S-bridged trinuclear structure. In deltadelta-[4](3+), a similar linear-type trinuclear structure is constructed from the delta-mer(S).trans(N(aet))-[Co(aet)(2)(pymt)] and delta-C(2)-cis(S)-[Co(aet)(2)(en)](+) units that are bound by a Pt(II) ion with a slightly distorted square-planar geometry through four aet S atoms.     

Structure and dynamics of binary and ternary lanthanide(III) and actinide(III) tris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione] (TTA) complexes. Part 2, the structure and dynamics of binary and ternary complexes in the Y(III)/Eu(III)-TTA-tributylphosphate (TBP) system in chloroform as studied by NMR spectroscopy

The stoichiometric reaction mechanisms, rate constants and activation parameters for inter- and intramolecular ligand exchange reactions in the binary Y/Eu(TTA)(3)(OH(2))(2)-HTTA and the ternary Y/Eu(TTA)(3)(OH(2))(2)-TBP systems have been studied in chloroform using (1)H and (31)P NMR methods. Most complexes contain coordinated water that is in very fast exchange with water in the chloroform solvent. The exchange reactions involving TTA/HTTA and TBP are also fast, but can be studied at lower temperature. The rate constant and activation parameters for the intramolecular exchange between two structure isomers in Y(TTA)(3)(OH(2))(2) and Y(TTA)(3)(TBP)(OH(2)) were determined from the line-broadening of the methine protons in coordinated TTA. The rate equations for the intermolecular exchange between coordinated TTA and free HTTA in both complexes are consistent with a two-step mechanism where the first step is a fast complex formation of HTTA, followed by a rate determining step involving proton transfer from coordinated HTTA to TTA. The rate constants for both the inter- and intramolecular exchange reactions are significantly smaller in the TBP system. The same is true for the activation parameters in the Y(TTA)(3)(OH(2))(2)-HTTA and the ternary Y/Eu(TTA)(3)(TBP)(OH(2))-HTTA systems, which are ΔH(≠) = 71.8 ± 2.8 kJ mol(-1), ΔS(≠) = 62.4 ± 10.3 J mol(-1) K(-1) and ΔH(≠) = 38.8 ± 0.6 kJ mol(-1), ΔS(≠) = -93.0 ± 3.3 J mol(-1) K(-1), respectively. The large difference in the activation parameters does not seem to be related to a difference in mechanism as judged by the rate equation; this point will be discussed in a following communication. The rate and mechanism for the exchange between free and coordinated TBP follows a two-step mechanism, involving the formation of Y(TTA)(3)(TBP)(2).     

Competitive Substitution and Electron Transfer in Reactions between Haloamminegold(III) and Halocyanoaurate(III) Complexes and Thiocyanate

Kinetics for reactions between thiocyanate and trans-Au(CN)(2)Cl(2)(-), trans-Au(CN)(2)Br(2)(-), and trans-Au(NH(3))(2)Cl(2)(+) in an acidic, 1.00 M perchlorate aqueous medium have been studied by use of conventional and diode-array UV/vis spectroscopy and high-pressure and sequential-mixing stopped-flow spectrophotometry. Initial, rapid formation of mixed halide-thiocyanate complexes of gold(III) is followed by slower reduction to Au(CN)(2)(-) and Au(NH(3))(2)(+), respectively. This is an intermolecular process, involving attack on the complex by outer-sphere thiocyanate. Second-order rate constants at 25.0 degrees C for reduction of trans-Au(CN)(2)XSCN(-) are (6.9 +/- 1.1) x 10(4) M(-)(1) s(-)(1) for X = Cl and (3.1 +/- 0.7) x 10(3) M(-)(1) s(-)(1) for X = Br. For reduction of trans-Au(CN)(2)(SCN)(2)(-) the second-order rate constant at 25.0 degrees C is (3.1 +/- 0.1) x 10(2) M(-)(1) s(-)(1) and the activation parameters are DeltaH() = (55 +/- 3) x 10(2) kJ mol(-)(1), DeltaS() = (-17.8 +/- 0.8) J K(-)(1) mol(-)(1), and DeltaV() = (-4.6 +/- 0.5) cm(3) mol(-)(1). The activation volume for substitution of one chloride on trans-Au(NH(3))(2)Cl(2)(+) is (-4.5 +/- 0.5) cm(3) mol(-)(1), and that for reduction of trans-Au(NH(3))(2)(SCN)(2)(+) (4.6 +/- 0.9) cm(3) mol(-)(1). The presence of pi-back-bonding cyanide ligands stabilizes the transition states for both substitution and reductive elimination reactions compared to ammine. In particular, complexes trans-Au(CN)(2)XSCN(-) with an unsymmetric electron distribution along the X-Au-SCN axis are reduced rapidly. The observed entropies and volumes of activation reflect large differences in the transition states for the reductive elimination and substitution processes, respectively, the former being more loosely bound, more sensitive to solvational changes, and probably not involving any large changes in the inner coordination sphere. A transition state with an S-S interaction between attacking and coordinated thiocyanate is suggested for the reduction. The stability constants for formation of the very short-lived complex trans-Au(CN)(2)(SCN)(2)(-) from trans-Au(CN)(2)X(SCN)(-) (X = Cl, Br) by replacement of halide by thiocyanate prior to reduction can be calculated from the redox kinetics data to be K(Cl,2) = (3.8 +/- 0.8) x 10(4) and K(Br,2) = (1.1 +/- 0.4) x 10(2).