Oxidative chemical or electrochemical

Meff 2-2 Mb g = 2.11, gx = 2.058. Similar complexes can be obtained with other ligands [63] some can be oxidized, chemically or electrochemically, to silver(III) complexes. 

The complexes [Os(LL)3] + can be oxidized chemically or electrochemically to [Os(LL)3] +, the Os couples being related to the photophysical behavior of the 2+ complexes. A substantial amount of work has been carried out on the outer-sphere electron transfer to [Os(LL)3] + (a good one-electron oxidant that is co-ordinatively stable) with a range of reductants such [Fe(CN)6]" (see Electron Transfer in Coordination Compounds). 

The tridentate macrocyclic ligands 1,4,7-triazacyclo-nonane and 1,4,7-trithiacyclononane (39, E = NH, S, respectively), act as bidentate chelates toward Pd(II) to give square-planar complexes [Pd L2] + with two pendant E donor atoms (40). The complexes can be oxidized chemically or electrochemically to [Pd L2] + (41) (equation 15), which show tetragonaUy elongated octahedral coordination, as expected for a Jahn-Teller distorted d complex. Interestingly, electrochemical stndies on the Pd(n) complexes (30) and (31) (Section 6.5) show that only the second can be reversibly oxidized to Pd(III). 

The TTF molecule (Chart 1) is a u-delocalized system with readily accessible redox states. TTF. TTF, and TTF ". The reduced form ftmctions as a n-donor in FF interactions, but the oxidized forms have n-acceptor character. Incorporation of one TTF moiety into a donor cycle also containing 1.5-dioxynaphthalene, and catenation with a Z /5 -4,4 -bipyridinium n-acceptor cycle, leads to a switchable [2]catenane (Fig. 10). In the reduced TTF form (Fig. 10b), the TTF molecule, as donor, is sandwiched between the two 4,4 -bipyridinium acceptors. When oxidized (chemically or electrochemically). so that the TTF has a positive or 2+ charge (Fig. 10a), electrostatics cause rotational translation of one cycle relative to the other to displace the positive TTF to the outer section of the catenane. This switching is reversible. 

The alkyne complexes [Ru(acac)2(< -RC=CC6H4NMe2)] (R = Ph 47a, SiMe3 47b, H 47c) can be reversibly oxidized chemically or electrochemically to the corresponding ruthenium(iii) cations. A comparison of the Ru(t7 -G=G) distances in the X-ray crystal structures for 47a and 47a reveals that the alkyne binds more strongly in the oxidized complex. ... 

Polyaniline" has been described in many papers [1-6] during the past 100 years or so. It has been reported as existing in various, usually ill-defined forms such as "aniline black", "emeraldine", "nigraniline", etc., synthesized by the oxidative chemical or electrochemical polymerization of aniline. Certain of these materials have been shown to have an unexpectedly high conductivity [2-6]. 

In particular poly(3,4-ethylenedioxythiophene) (PEDOT) widely used can be synthesized by oxidative chemical or electrochemical polymerisation producing thin films that are optically transparent in the reduction state and light blue color in the oxidized state with high stability and conductivity. The most common dopant for PEDOT is polystyrene sulfonate (PSS) rendering a water-soluble compound [102]. 

The most stable (and therefore the most intensely studied) EAPs are the oxidized, cationic salts of highly conjugated polymers, although stability varies widely with chemical composition. Some cationic salts are quite stable in air (40), while others are highly reactive. The cationic salts (or p-doped polymers) are obtained by oxidation (chemical or electrochemical) of neutral polymers or of monomers. Chemical oxidation in this context refers to the removal of electrons using a chemical oxidant such as ferric chloride (43), whereas... 

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