Non-Redox Routes

Organic salts of [Zn(dmit)2 2 readily undergo dithiolene-transfer reactions with metal chlorides. For example, this dianion reacts with Cp2TiCl2, NbCl5, 

and AuCl(PPh3) to afford Cp2Ti(dmit) (92, 117), [V(dmit)3 2 (191), 

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The substitution of a methyl ligand in [AuMe3(PR3)] by a benzenethiolato-ligand goes via a non-redox radical route. This contrasts with analogous reactions at platinum(u), which can proceed via an oxidative addition path. However, the reaction... 

Because of possible catalytic and biological relevance of metal-sulfur clusters, several such compounds of cobalt have been prepared. The action of H2S or M2S (M = alkali metal) on a non-aqueous solution of a convenient cobalt compound (often containing, or in the presence of, a phosphine) is a typical route. Diamagnetic [Co6Ss(PR3)6] (R = Et, Ph) comprise an octahedral array of metal atoms (Co-Co in the range 281.7 to 289.4pm), all faces capped by atoms,and show facile redox behaviour... 

Ligands such as aniline (an), 1,2-diaminobenzene (dab, o-phenylenediamine) and 2,2 -dia-minobiphenyl886 887 are classed separately, not because their ability to bind to a central metal is any less than the ligands discussed previously, but because of their potential non-innocent behavior888 with respect to internal redox reactions. Indeed, the dark blue complex isolated from the air oxidation of Con/dab in aqueous ethanol (a conventional route to yellow Co(diamine)3+ systems) has been shown to have structure (117) with five-coordinate Co11.888 Related diimine complexes have been reported for Ni11889 as well as the conventional Ni(dab)(+,890 Co(dab)3+ 891 and Pt(dab) + 892 systems. 

Numerous examples exist of combining CRP methods with other polymerization techniques for preparation of block copolymers. Non-living polymerization methods like condensation, free-radical, and redox processes can easily be combined with CRP to produce novel materials. Transformation chemistry may be the only route to incorporate polymers like polysulfones (as described above), polyesters, or polyamides that are prepared solely through condensation processes into subsequent CRP to form block copolymers with vinyl monomers. The same can be said of polymers prepared through coupling techniques, like po-ly(phenylenevinylene) and poly(methylphenylsilylene), which can maintain their conductive or photoluminescence properties, but become easier to process... 

Composition of the inorganic framework can be varied just like the surfactant use has been expanded beyond the original cationic species. The number of explored element combinations has been enormous and often driven by specific catalytic needs and prior experience with amorphous or crystalline compositions [37]. One of the leading approaches was doping of silica formulation with appropriate activating clement, such as aluminum (lo impart acidity) and titanium or vanadium for redox potential. Based on analogy of AlPO s and SAPO s to zeolites these compositions were also synthesized in the mesoporous form as were other non-silica inorganic oxides and their combinations [38]. Pure metal mesoporous product was obtained via the pre-formed liquid crystal route 1391. 

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