Hexaaqua

Rhodium complexes with oxygen ligands, not nearly as numerous as those with amine and phosphine complexes, do, however, exist. A variety of compounds are known, iucluding [Rh(ox)3] [18307-26-1], [Rh(acac)3] [14284-92-5], the hexaaqua ion [Rh(OH2)3] [16920-31 -3], and Schiff base complexes. Soluble rhodium sulfate, Rh2(804 )3-a H2 0, exists iu a yellow form [15274-75-6], which probably coutaius [Rh(H20)3], and a red form [15274-78-9], which contains coordinated sulfate (125). The stmcture of the soluble nitrate [Rh(N03)3 2H20 [10139-58-9] is also complex (126). Another... 

Table 4. Water Exchange Rates and Activation Parameters of Hexaaqua Complexes at 25°C, ...

Nickel, diiodotris(trimethyl phosphite)-strpeture, 1,45 Nickel, hcxaamminc-rcactions, 1,27 Nickel, hexaaqua-reactions, 1, 204 Nickel, hexafluoro-, 5,186 Nickel, hexakis(A, Ar -dimethylurea)-tetrachloronickelate isomerization, 1,470... 

Consider some vanadium ions in aqueous solution. Pale violet solutions of vanadium(ii) salts contain the [V(H20)6] ion. The vanadium(ii) center is only weakly polarizing, and the hexaaqua ion is the dominant solution species. Aqueous vanadium(ii) solutions are observed to be unstable with respect to reduction of water by the metal center. In contrast, vanadium(ni) is more highly polarizing and an equilibrium between the hexaaqua and pentaaquahydroxy ion is set up. The of 2.9 means that the [V(OH2)6] ion (Eq. 9.17) only exists in strongly acidic solution or in stabilizing crystal lattices. 

Color is a spectacular property of coordination complexes. For example, the hexaaqua cations of 3 transition metals display colors ranging from orange through violet (see photo at right). The origin of these colors lies in the d orbital energy differences and can be understood using crystal field theory. 

C20-0015. Explain why hexacyano complexes of metals in their +2 oxidation state are usually yellow, but the corresponding hexaaqua compounds are often blue or green. 

Due to the high charge-to-radius ratio, a hexaaqua Cr(III) cation loses protons to form olates (3atb) in this hydrolysis process. One, two and three protons can be lost from Cr-coordinated HgO to yield the mono-, di- and tri- hydroxides of hydrous Cr species,... 

Olated Cr(III) reagents were prepared according to Equation 2 by reacting CrtNOg) with a calculated equivalent of NaOH. Chromic nitrate was used Decause the freshly prepared solution affords the hexaaqua Cr(III) cations. 

The implications of these mechanistic studies for our understanding of environmental iron sequestration by siderophores is as follows. The hydroxyl containing aqua ferric ions will tend to form ferri-siderophore complexes more rapidly than the hexaaqua ion and ferrous ion will be sequestered more rapidly than the ferric ion. However, once in a siderophore binding site the ferrous ion will be air oxidized to the ferric ion, due to the negative redox potentials (see Section III.D). This also means that Fe dissolution from rocks will be influenced by mineral composition (other donors in the first coordination shell) as well as surface reductases in contact with the rock, and of course surface area (4,13). 

Fig. 8. Energies calculated with a polarizable continuum model, differences of the sums of all metal-oxygen bond lengths, AS(M-O), and energy profiles for water exchange on rhodium(III) and ruthenium(II) hexaaqua ions.

Iron(II) formate dihydrate, 14 537 Iron(II) fumarate, 14 537 Iron gelbs, 19 399, 400 Irondl) gluconate dihydrate, 14 541 Iron group carbides, 4 690-692 Iron halides, 14 537-540 Iron hydroxide, water exchange rates and activation parameters of hexaaqua complexes, 7 589t Iron(II) hydroxide, 14 542 Iron(III) hydroxide, 14 542 Iron hydroxides, 14 541—542 Iron(II) iodide, 14 540 Iron(III) iodide, 14 540 Iron/iron alloy plating, 9 813—814. See also Fe entries... 

Rate Constants and Activation Parameters for Water Exchange on Hexaaqua and Monohydroxy Pentaaqua Trivalent Metal Ions ... 

The values obtained for the proton transfer in these four systems (Table IV) are typically as expected for these rapid processes. Examples from the literature where similar reactions were studied in metal complexes include the [Cr(OH)(OH2)]2+ (62) and [VO(OH2)5]2+ (63) systems. In the proton exchange study of the hexaaqua aluminate(III) system a bimolecular process, similar to that proposed for the systems in this study, for the exchange between the [Al(OH2)6]3+ and [Al(OH2)5(OH)]2+ (64) complexes was postulated. 

The Homogeneous Case. Margerum (1978) and Hering and Morel (1990) have elaborated on mechanisms and rates of metal complexation reactions in solution. In the Eigen mechanism, formation of an outer-sphere complex between a metal and a ligand is followed by a rate limiting loss of water from the inner coordination sphere of the metal, Thus, for a bivalent hexaaqua metal ion... 

ESR and ESEM studies of Cu(II) in a series of alkali metal ion-exchanged Tl-X zeolites were able to demonstrate the influence of mixed co-cations on the coordination and location of Cu(II) (60). The presence of Tl(l) forces of Cu(II) into the -cage to form a hexaaqua species, whereas Na and K result in the formation of triaqua or monoaqua species. In NaTl-X zeolite, both species are present with the same intensity, indicating that both cations can influence the location and coordination geometry of Cu(II). The Cu(II) species observed after dehydration of Tl-rich NaTl-X and KT1-X zeolites was able to interact with ethanol and DMSO adsorbates but no such interaction was observed with CsTl-X zeolites. This interaction with polar adsorbates was interpreted in terms of migrations of the copper from the -cages. 

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