Partial molal volumes for iron(II)-diimine complexes in water and in aqueous methanol

Summary Partial molal volumes of the perchlorate or chloride salts of several tris-diimine-iron(II) cations have been determined in aqueous and methanol-water solutions by vibrating-tube densimetry. Partial molal volumes of the cations at infinite dilution have been estimated for aqueous solution, and compared with values for related cations. Trends of limiting partial molal volumes for perchlorate salts in methanol-water media are compared with trends in transfer chemical potentials for the respective cations; both are discussed in terms of ligand-dependent preferential solvation behaviour.     

Transfer chemical potentials for cobalt(III) and chromium(III) complexes from water into aqueous methanol; their relevance to reactivity trends for cobalt(III)-chloride aquation

Summary We report solubilities of a number of cobalt(III) and chromium(III) complex salts in methanol-water mixtures. From these, and published solubilities of salts of other complexes of these metals, we have calculated transfer chemical potentials from water into aqueous methanol for a variety of cationic and anionic complexes of cobalt(III) and chromium(III), using the assumption _m(Ph₄As⁺) + _m(BPh ₄ ^– ). The established trends are discussed in terms of electrostatic factors and of the hydrophilicity or hydrophobicity of the ligands present. The effects of single ion assumptions on conclusions of initial state-transition state analyses of solvent effects on reactivity are assessed with particular reference to aquation of thetrans-[Co(en)₂Cl₂]⁺ andtrans-[Co(py)₄Cl₂]⁺ cations.On leave from the Faculty of Science, Sohag, Egypt.     

Solubilities of salts of cobalt(III), chromium(III), and iron(II) complexes in aqueous methanol; transfer chemical potentials of anions

Summary We report solubilities of a variety of salts of cobalt(III), chromium(III), and iron(II) complexes in methanol-water mixtures at 298.2K. From these solubilities and published transfer chemical potentials for the complex cations we are able to derive transfer chemical potentials for such anions as nitrate, thiosulphate, peroxodisulphate, dithionate, thiocyanate, and antimonyl tartrate. Transfer chemical potentials for several hexahalogenometallate anions, and tetrachloroplatinate(II), are derived from published solubilities. A comparative picture of transfer chemical potentials for anions is thus available, with the transition metal complex anions in the overall context of anions and their solvation characteristics in methanol-water mixtures.On leave from the Faculty of Science, Sohag, Egypt.     

Iron(II)-diimine complexes: solvatochromism and reactivity

Summary Reactivity trends are reported for aquation of tris(5-nitro-1,10-phenanthroline)iron(II) in ternary H₂O-t-BuOH-polyethyleneglycol (PEG400) solvent media. Wavelengths of maximum absorption for the lowest energy charge-transfer band of dicyanobis(2-acetylpyridineoximato)-iron(II) are reported for the same series of ternary solvent mixtures. There is no overall correlation of rate constants with wavelength shifts, indicating that solvation effects in the two systems are not directly related.On leave from the Faculty of Science, Assiut University, Sohag, Egypt.     

Solvation of inorganic complexes: transfer chemical potentials for mono- and bi-nuclear cobalt(III) complexes to methanol + water mixtures

Solubilities in MeOH--H₂O mixtures at 298.2 K are reported for a number of salts of mono- and bi-nuclear cobalt(III) complexes. From these solubilities and published single ion transfer chemical potentials, on the TPTB (Ph₄P⁺ = BPh^– ₄ ) assumption, transfer chemical potentials have been derived for these mono- and bi-nuclear cobalt(III) complexes. The results and trends are discussed in relation to those for other complexes and ions in these binary aqueous solvent mixtures.     

Uncharged encapsulated iron(II) complexes: transfer chemical potentials and solvation in water-methanol and water-t-butanol mixtures

Summary Transfer chemical potentials have been determined from measured solubilities for four uncharged encapsulated iron(II) complexes containing three diimine ligating moieties and O₃BOBu-n and O₃BF capping groups, in H₂O–MeOH andt-BuOH–H₂O solvent mixtures, The trends in transfer chemical potentials are discussed in terms of the natures of the encapsulating ligands, and are compared with those for a selection of other iron(II)-diimine complexes.     

Rate constant for water loss from low-spin iron(II) in aquapentacyanoferrate(II)

Rate constants for the reaction of [Fe(CN)₅(H₂O)]^–3 with [Co(NH₃)₅(pyrazine)]³⁺ have been analysed on the basis of a pre-association equilibrium constant and a rate constant for the subsequent ligand interchange. The latter represents an unusual parameter, a rate constant for water loss from a low-spin iron(II) centre.     

Structure of iron (II) and cobalt (II) bromide complexes in aqueous solution by X-ray diffraction analysis

Structures of bromo-metal complexes in concentrated aqueous solutions of FeBr₂ and of CoBr₂ were investigated by X-ray diffraction analysis. The complexes possess an octahedral geometry coordinating Br^– along with H₂O ligands. The frequency factors of metal-Br contacts per one atom of metal were 0.325 for the 2.7M (mol-dm^–3) and 0.747 for the 4.5M FeBr₂ solutions, and 0.280 for the 2.8M and 0.595 for the 4.3M CoBr₂ solutions. The frequency factors suggested that the tendency of metal ions to forming monobromo complexes is in the order, Fe>Co>Ni相似文献   

Systematic structural control of multichromic platinum(II)-diimine complexes ranging from ionic solid to coordination polymer

Reactions of a Pt(II)-diimine-based metalloligand Na(2)[Pt(CN)(2)(4,4'-dcbpy)] (4,4'-H(2)dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) with alkaline-earth metal salts Mg(NO(3))(2)·6H(2)O, CaCl(2), SrCl(2)·6H(2)O, and BaBr(2)·2H(2)O in aqueous solution gave luminescent complexes formulated as [Mg(H(2)O)(5)][Pt(CN)(2)(4,4'-dcbpy)]·4H(2)O (MgPt-4·9H(2)O), {[Ca(H(2)O)(3)][Pt(CN)(2)(4,4'-dcbpy)]·3H(2)O}(∞) (CaPt-4·6H(2)O), {[Sr(H(2)O)(2)][Pt(CN)(2)(4,4'-dcbpy)]·H(2)O}(∞) (SrPt-4·3H(2)O), and {[Ba(H(2)O)(2)][Pt(CN)(2)(4,4'-dcbpy)]·3H(2)O}(∞) (BaPt-4·5H(2)O), respectively. The crystal structures of all MPt-4 complexes were determined by X-ray crystallography. In these structures, the alkaline-earth metal ions are commonly coordinated to the carboxyl groups of the [Pt(CN)(2)(4,4'-dcbpy)](2-) metalloligand. In the case of MgPt-4·9H(2)O, the Mg(II) ion is bound by five water molecules and one oxygen atom of a carboxyl group to form a neutral complex molecule [Mg(H(2)O)(5)][Pt(CN)(2)(4,4'-dcbpy)]. In contrast, the alkaline-earth metal ion and metalloligand form two-dimensional (CaPt-4·6H(2)O) and three-dimensional (SrPt-4·3H(2)O and BaPt-4·5H(2)O) coordination networks, respectively. All fully hydrated complexes exhibited a strong phosphorescence from the triplet π-π* transition state. Luminescence spectroscopy revealed that MgPt-4·9H(2)O exhibited interesting multichromic (i.e., thermo-, mechano-, and vapochromic) luminescence, whereas CaPt-4·6H(2)O showed only thermochromic luminescence. The other two complexes did not exhibit any chromic behaviour. Combination analysis of powder X-ray diffraction, thermogravimetry, and IR spectroscopy suggests that the dimensionality of the coordination network contributes considerably to both the structural flexibility and luminescence properties; that is, the low-dimensional flexible coordination network formed in MPt-4 complexes with smaller alkaline-earth metal ions enables a structural rearrangement induced by thermal and mechanical stimuli and vapour adsorption, resulting in the observed multichromic behaviour.     

Unusual iron(II) and cobalt(II) complexes derived from monodentate arylamido ligands

The coordination chemistry of the N-substituted arylamido ligands [N(R)(C6H3R'2-2,6)] [R = SiMe3, R' = Me (L1); R = CH2But, R' = Pri (L2)] toward FeII and CoII ions was studied. The monoamido complexes [M(L1)(Cl)(tmeda)] [M = Fe (1), Co (2)] react readily with MeLi, affording the mononuclear, paramagnetic iron(II) and cobalt(II) methyl-arylamido complexes [M(L1)(Me)(tmeda)] [M = Fe (3), Co (4)]. Treatment of 2:1 [Li(L2)(THF)2]/FeCl2 affords the unusual two-coordinate iron(II) bis(arylamide) [Fe(L2)2] (5).     

Mechanistic studies of nitric oxide reactions with water soluble iron(II), cobalt(II), and iron(III) porphyrin complexes in aqueous solutions: implications for biological activity.

The reactions of nitric oxide and carbon monoxide with water soluble iron and cobalt porphyrin complexes were investigated over the temperature range 298-318 K and the hydrostatic pressure range 0.1-250 MPa [porphyrin ligands: TPPS = tetra-meso-(4-sulfonatophenyl)porphinate and TMPS = tetra-meso-(sulfonatomesityl)porphinate]. Large and positive DeltaS(double dagger) and DeltaV(double dagger) values were observed for NO binding to and release from iron(III) complexes Fe(III)(TPPS) and Fe(III)(TMPS) consistent with a dissociative ligand exchange mechanism where the lability of coordinated water dominates the reactivity with NO. Small positive values for Delta and Delta for the fast reactions of NO with the iron(II) and cobalt(II) analogues (k(on) = 1.5 x 10(9) and 1.9 x 10(9) M(-1) s(-1) for Fe(II)(TPPS) and Co(II)(TPPS), respectively) indicate a mechanism dominated by diffusion processes in these cases. However, reaction of CO with the Fe(II) complexes (k(on) = 3.6 x 10(7) M(-1) s(-1) for Fe(II)(TPPS)) displays negative Delta and Delta values, consistent with a mechanism dominated by activation rather than diffusion terms. Measurements of NO dissociation rates from Fe(II)(TPPS)(NO) and Co(II)(TPPS)(NO) by trapping free NO gave k(off) values of 6.3 x 10(-4) s(-1) and 1.5 x 10(-4) s(-1). The respective M(II)(TPPS)(NO) formation constants calculated from k(on)/k(off) ratios were 2.4 x 10(12) and 1.3 x 10(13) M(-1), many orders of magnitude larger than that (1.1 x 10(3) M(-1)) for the reaction of Fe(III)(TPPS) with NO.     

Spin transition in iron(III) and iron(II) complexes

The main stages of the studies on the spin transitions in iron(III) and iron(II) complexes are considered. The types of the spin transitions and the factors responsible for the latter are reported. The problems arising during experiments in this field are discussed.     

Gaseous iron(II) and iron(III) complexes with BINOLate ligands

Electrospray ionization (ESI) of dilute solutions of 1,1'-bi-2-naphthol (BINOL) and iron(II) or iron(III) sulfate in methanol/water allows the generation of monocationic complexes of iron and deprotonated BINOL ligands with additional methanol molecules in the coordination sphere, and the types of complexes formed can be controlled by the valence of the iron precursors used in ESI. Thus, iron(II) sulfate leads to [(BINOLate)Fe(CH3OH)n]+ complexes (n=0-3), whereas usage of iron(III) sulfate allows the generation of [(BINOLdiate)-Fe(CH3OH)n]+ cations (n=0-2); here, BINOLate and BINOLdiate stand for singly and doubly deprotonated BINOL, respectively. Upon collision-induced dissociation, the mass-selected ions with n>0 first lose the methanol ligands and then undergo characteristic fragmentations. Bare [(BINOLdiate)Fe]+, a formal iron(III) species, undergoes decarbonylation, which is known as a typical fragmentation of ionized phenols and phenolates either as free species or as the corresponding metal complexes. The bare [(BINOLate)Fe]+ cation, on the other hand, preferentially loses neutral FeOH to afford an organic C20H12O+* cation radical, which most likely corresponds to ionized 1,1'-dinaphthofurane.     

Solid complexes of iron(II) and iron(III) with rutin

Solid complex compounds of Fe(II) and Fe(III) ions with rutin were obtained. On the basis of the elementary analysis and thermogravimetric investigation, the following composition of the compounds was determined: (1) FeOH(C₂₇H₂₉O₁₆)·5H₂O, (2) Fe₂OH(C₂₇H₂₇O₁₆)·9H₂O, (3) Fe(OH)₂(C₂₇H₂₉O₁₆)·8H₂O, (4) [Fe₆(OH)₂(4H₂O)(C₁₅H₇O₁₂)SO₄]·10H₂O. The coordination site in a rutin molecule was established on the basis of spectroscopic data (UV–Vis and IR). It was supposed that rutin was bound to the iron ions via 4C=O and 5C—oxygen in the case of (1) and (3). Groups 5C–OH and 4C=O as well as 3′C–OH and 4′C–OH of the ligand participate in binding metals ions in the case of (2). At an excess of iron(III) ions with regard to rutin under the synthesis conditions of (4), a side reaction of ligand oxidation occurs. In this compound, the ligands’ role plays a quinone which arose after rutin oxidation and the substitution of Fe(II) and Fe(III) ions takes place in 4C=O, 5C–OH as well as 4′C–OH, 3′C–OH ligands groups. The magnetic measurements indicated that (1) and (3) are high-spin complexes.     

Alkyl isomerisation in three-coordinate iron(II) complexes

The tertiary to iso-butyl isomerisation of three-coordinate iron(II) diketiminate complexes is reported and a hydride intermediate is proposed on the basis of exchange experiments.     

Radiation synthesis of iron(II) and ruthenium(II) alkylnitroso complexes

The radiolysis of deoxygenated aqueous solutions of Ru(NH₃)₅NO³⁺ and Fe(CN)₅NO²⁻ in the presence of organic compounds (RH) generates alkylnitroso complexes of the form Ru(NH₃)₅N(O)R²⁺ and Fe(CN)₅N(O)R³⁻ where RH = tert-butyl alcohol, tert-butyl amine, N,N-dimethylacetamide, α-aminoisobutyric acid, pivalic acid, and α-hydroxyisobutyric acid. The products form from the rapid combination of the β-carbon radical derived from the reaction of the organic compound with OH radicals (OH + RH → R· + H₂O) and the one-electron reduced metal complex formed by interaction with e_aq⁻: Ru(NH₃)₅NO³⁺ + e_aq⁻ → Ru(NH₃)₅NO²⁺; Fe(CN)₅NO²⁻ + e_aq⁻ → Fe(CN)₅NO³⁻. The alkylnitroso complexes are moderately O₂-insensitive but display varying degrees of thermal stability. Stability permitting, these complexes have been characterized by ion-exchange chromatography and UV-vis-IR spectroscopy. The green ruthenium complexes exhibit λ_max 740 and 342 nm (ϵ 22 and 4.5 × 10³ M⁻¹ cm⁻¹, respectively) and ν_NO in the 1365–1405 cm⁻¹ region. The less stable red iron analogues absorb at 475 and ∼ 250 nm (ϵ 5.0 × 10³ and ∼ 9 × 10³ M⁻¹ cm⁻¹, respectively).