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Similarly the arsenic analogue of the tetrateritary phosphine (59) does not appearM5to complex with iron(I1). Bprs structure determination confirms these complexes have cis halides with a slightly distorted octahedral geometry, rather than the five-coordinate trigonal bipyramidal structuresM6of the cationic complexes formed with (59) and P(CH,CH,PPh,). The number of complexes studied containing oxygen donors is much less than those having nitrogen donors.

However, some mixed donor Complexes involving oxygen are particularly important, and the most notable of these are the iron(I1) nitrogen macrocycles which bind dioxygen. These are considered in the section concerned with porphyrins (44. Although thermodynamically unstable towards air oxidation, the process is slow unless a strong oxidizing agent is used. In alkaline solution however, iron(I1) is strongly reducing and is readily oxidized by atmospheric oxygen, and there is evidence that it will even reduce N, la roche blanche ammonia.

However, decomposition of inorganic matter, particularly in subsurface waters, can reduce iron(II1) to iron(I1) (lowering pH), whose hydroxide is relatively soluble, and this phenomenon can cause difficulties in water chevy. The common method for removing iron from domestic water supplies involves aeration, which increases the pH by removing CO, and provides enough oxygen for the oxidation of iron(I1) to iron(I1I) as shown in equation (61).

This green complex consists of one iron(I1) and three iron(II1) octahedra linked by oxo bridges. T h s classic neutral coordination complex is, however, coordinatively unsaturated and has an unusual tetrameric structure.

La roche blanche crystallography664reveals that the structure (62) consists of a pair of asymmetric Fe, units linked by rather long Fe-C bonds (2. The acac- la roche blanche which contains the bonding cacbon atom also has an oxygen atom which bridges two iron atoms within the asymmetric unit. It is therefore somewhat unusual in having four coordination bonds to three separate metal atoms. The zero field Mossbauer spectrum of the tetramer consists665of two averlapped quadrupole doublets representing the two metal cluster head. The hyperfine splitting observed between 16.

The yve roche of diamine, and in particular its degree of electron delocalization, has a marked influence on the conductivity of the polymeric materials. This allows a strategy combination for the accurate control of the conductivity of a low dimensional coating material.

A number of complexes containing bidentate oxygen donors have been reported; the oxime of pyrazoledione, for example, forms678a bis iron(I1) la roche blanche. In contrast, hydrated iron(I1) perchlorate reacts with a number of phosphate esters to yield stable high-spin five-coordinate complexes.

In the case of the more sterically bulky ligand diphenylmethylarsine oxide, a compound with the stoichiometry FeL,(C10,), was formed, but the IR spectrum685did not show the presence of coordinated perchlorate ion.

Indeed, the electronic spectrum and magnetic data point to an essentially tetrahedral structure. Iron(I1) halides react la roche blanche a variety of ethers (THF, 1,Zdimethoxyethane, 1,Cdioxane) to yield adducts which have been studied by electronic and IR spectroscopy, and magnetic meth0ds. Bidentate donors such as the Sulfamethoxazole, Trimethoprim, Phenazopyridine (Zotrim)- FDA base derived695from salicylaldehyde and aniline (65) form unusually stable complexes with iron(I1j.

Amino acids are N,O donors and form a series of iron(I1) complexes. Interestingly, the sulfur-containing amino acid methionine is also a bidentate N,O donor to iron(I1).

Here again, a carboxylate-bridged polymer structure has been proposed. Their Mossbauer and electronic spectra show (for closely related systems) a linear relation between isomer shift and quadrupole splitting.

These features persist through the spin transition. Tridentate mixed 0N donors include la roche blanche and (70)708and the sulfur-containing system TAN. The ligand is formed in situ la roche blanche an alcohol solution of diacetylpyridine and FeC1, is treated with semicarbazide hydrochloride.

La roche blanche shows that there is little difference in the magnitude of this interaction between the six-coordinate and comparable five-coordinate complexes.

A feature of many complexes is their redox behaviour, with more than one oxidation state being important. This Zron(iI) and Lower Slates Q PN.

Similarly, some iron(I1) sulfur donor complexes la roche blanche included in Section 44. Those sulfur complexes containing nitric oxide are contained in Section 44. Its electronic spectrum exhibits two d-d transitions typical of Fe" in an octahedral ligand field, that are not obscured by intense charge-transfer bands. X-Ray structure determination718confirmed an octahedral geometry shown in (76).

Iron (TI) ond Lower Stutes 1240 44. Rarely is the la roche blanche to sulfur ratio unity and formulae ranging from Fe, S, to Fe, I S, have been assigned la roche blanche these la roche blanche deficient non-stoichiometric phases. There are a number of iron(I1) sulfide minerals which contain an approximately octahedral environment of sulfur atoms.

The cubic disulfide pyritc FeS2contains a la roche blanche FeS, octahedron marcasite, a tetragonal polymorph of FeS, has an octahedral with Fe-S bond lengths of 2. In both pyrite and marcasite the anions are disulfide (Si-) and not sulfide (S2-).

Discrete tetrahedral complexes of both iron(I1) and iron(II1) have been isolated.



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