Ferrocene various complexes

Of particular interest are various complexes formed by organoboron compounds with transition elements. Treatment of the N-lithio-derivative of the S>membered boron-nitrogen heterocycle, 7.28, with anhydrous ferrous chloride yields a dark-brown diamagnetic product, for which the sandwich ferrocene-like structure 7.29, has been proposed. 

The rhodium complexes of the ferrocene derivatives 39 have shown useful characteristics for the reduction of itaconates as well as dehydroamino acid derivatives [15, 167-170]. These compounds are hybrids between ferrocene-based ligands and the various other types. The P-chiral compounds, which in some ways are DIPAMP hybrids, showed tolerance for the reduction of N-methyl en-amides to produce N-methyl-a-amino acid derivatives [169-171]. 

Two classes of material will be described here - the metal dithiolenes and rare earth metallocenes. In the metal dithiolenes a strong, low energy pi-pi transistion occurs in the near IR (9.10). This can be tuned from about 700 nm to 1400 nm by altering the metal ion, substituents or charge state of the dithiolene. The dithiolenes are particularly attractive because of their optical stability which has been exploited in their use as laser Q-switch materials. In the rare earth complexes the near IR band is provided by/-/transistions of the rare earth ion rather than the cyclopentadienyl ring structure various nonlinear optical phenomena have been observed in glasses incorporating similar ions. Previous studies have shown that dicyclopentadienyl complexes such as ferrocene have off-resonant nonlinearities similar to nitrobenzene or carbon disulphide (11-13)... 

Besides the ferrocene crown ether ligands described earlier, a variety of related macrocyclic ferrocenophanes containing various sulfur, oxygen, and nitrogen heteroatoms have been reported by a number of groups (110-115) (Scheme 21). These ligands complex transition metal guest cations such as Ag(I), Cu(I), and Pd(II) (116,117). Of particular... 

Fluoride anion strongly interacts with various inorganic and organic boron and silicon compounds. These reactions are the basis for several fluoride sensors. Interaction of fluoride with boron compounds results in electron density redistribution and may also induce structural changes. Formation of fluoride complex by ferrocene derivative (Figure 16.19a) results in a decrease of oxidation potential by 200 mV... 

A number of molecular mechanics studies of metal cyclopentadienyl complexes have been reported recently. The systems studied include linear metallocenes (in particular ferrocene), ferrocene derivatives (such as complexes with substituted cyclopentadienyl ligands, bis(fulvalene)diiron complexes, ferrocenophanes and mixed ligand complexes with carbonyls and phosphines), and non-linear cyclopentadienyl complexes with various metal centers110, 127,15 >439 452(... 

Photochemical activation (15) and thermal activation (11,16, 17) of iron carbonyl complexes In various zeolites have been reported. Part of our study Is to use Mossbauer spectroscopy to Investigate the behavior of Fe(C0)5 on several zeolites when activated photochemically and thermally. Another part of our study Is to Investigate the novel preparation method of Scherzer and Fort (18) that Introduces iron Into (in their study) zeolite NH Y as an anionic complex. Finally, we will report the preparation of ferrocene sublimed onto zeolite ZSM-5. The photochemical and thermal activation of these systems will be reported as well as preliminary results of the photochemical isomerization of olefins by Fe(C0)5 zeolites and the thermal activation of Fischer-Tropsch catalytic systems. It also should be noted here that our Mossbauer studies involve an in-situ pretreatment cell which can be heated to 500°C under various gaseous atmospheres. 

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