Fe-complexes

Fe " complexes in general have magnetic moments at room temperature which are close to 5.92 BM if they are high-spin and somewhat in excess of 2BM (due to orbital contribution) if they are low-spin. A number of complexes, however, were prepared in 1931 by L. Cambi and found to have moments intermediate between these extremes. They are the iron(lll)-A,A-dialkyldithiocarbamates, [Fe(S2CNR2)3], in which the ligands are ... 

Most Fe complexes are octahedral but several other stereochemistries are known (Table 25.3). [FeX4] (X = Cl, Br, I, NCS) are tetrahedral. A single absorption around 4000 cm due to the T2 E transition is as expected, but magnetic moments of these and other apparently tetrahedral complexes are reported to lie in the range 5.0-5.4BM, and the higher values are difficult to explain. 

C id —75 C depending on the con und, Ihe moiwnt quite suddenly rises lo over 5BM. Confirmation of ibe transition in these and other Fe" complexes I,as been provided bv elecironic and Mossbaiier spectrasiopy. 

It is relevant to note at this point that, because the metal ions are isoelcctronic, the spectra of low-spin Fe complexes might be expected to be similar to those of low-spin Co ". However, Fe" requires a much stronger crystal field to effect spin-pairing and the ligands which provide such a field also give rise to low-energy charge-transfer bands which almost always obscure the d-d bands. Nevertheless, the spectrum of the pale-yellow [Fe(CN)f,] shows a shoulder at... 

Kiindig et al. recently applied the same perfluoroaryldiphosphonite ligand to the preparation of a cationic Ru catalyst 14 [20] (Scheme 1.27, Table 1.11). This catalyst also promotes the Diels-Alder reaction of a-bromoacrolein and cyclopenta-diene, although this Diels-Alder reaction is slower than that catalyzed by the analogous cationic Fe complex 13, and gives the cycloadducts with lower enantioselec-tivity (Fe 97% ee, Ru 92% ee). 

Crown thiaethers can form mono- or fe-complexes, depending upon the number of sulphurs in the ring (Figure 3.69). 

Prior to our work, Helling had reacted a series of hard carbanions with [Fe(mesitylene)2]++ (PFg )2 to obtain an attack on each ring giving the bis(cy-clohexadienyl)Fe" complex [31], Eq. (1). Stabilized carbanions reacted only once [31, 32] first step of Eq. (1) ... 

Compounds 167-171 outlined in Fig. 43 form another series of diboronic acids that form complexes with mono- and disaccharides. In these cases the asymmetrical immobilization of chromophoric functional groups, e.g., aromatic rings in 167-170 or Fe -complexation with the related boronate 171, can be analyzed by circular dichroism measurements [256-262]. 

Complex 5 was more active than the well-known precious-metal catalysts (palladium on activated carbon Pd/C, the Wilkinson catalyst RhCl(PPh3)3, and Crabtree s catalyst [lr(cod)(PCy3)py]PFg) and the analogous Ai-coordinated Fe complexes 6-8 [29] for the hydrogenation of 1-hexene (Table 2). In mechanistic studies, the NMR data revealed that 5 was converted into the dihydrogen complex 9 via the monodinitrogen complex under hydrogen atmosphere (Scheme 4). 

Scheme 21 Hydrosilylation catalyzed by an Fe complex with phosphorus ligands...

In 2008, Gade and coworkers reported that the asymmetric hydrosilylation of ketones was catalyzed by the Fe complex with a highly modular class of pincer-type ligand (Scheme 22) [71]. This Fe catalyst system showed both moderate to good... 

Scheme 22 Asymmetric hydrosilylation catalyzed by the Fe complex with the pincer-type ligand...

Our groups developed a catalytic C-CN bond cleavage of organonitriles catalyzed by the Fe complex (Scheme 49) [163, 164]. In this reaction, an organonitrile R-CN and EtsSiH are converted into EtsSiCN as a result of the C-CN bond cleavage and the Si-CN bond formation, and the R-H product. This is the first example of the catalytic C-CN bond cleavage of acetonitrile. 

Heterodinuclear Ni-Fe complexes, which are not stabilized by the phosphine and NO ligands, were synthesized by Tatsumi and coworkers as [NiFe] hydrogenase mimics [208-210]. Several examples are shown in Fig. 8. However, the catalytic activities of these complexes are not ascertained. 

To mimic the square-pyramidal coordination of iron bleomycin, a series of iron (Il)complexes with pyridine-containing macrocycles 4 was synthesized and used for the epoxidation of alkenes with H2O2 (Scheme 4) [35]. These macrocycles bear an aminopropyl pendant arm and in presence of poorly coordinating acids like triflic acid a reversible dissociation of the arm is possible and the catalytic active species is formed. These complexes perform well in alkene epoxidations (66-89% yield with 90-98% selectivity in 5 min at room temperature). Furthermore, recyclable terpyridines 5 lead to highly active Fe -complexes, which show good to excellent results (up to 96% yield) for the epoxidation with oxone at room temperature (Scheme 4) [36]. 

Remarkably, the shown Fe ° complexes reacted directly with oxygen to afford high-valent oxo-iron species. In addition, Kim, Nam, and coworkers explored... 

Among several applications, Fe-based hydrogenases play a central role in the stepwise reduction of CO2 to methane. This process is accomplished through various types of Fe-hydrogenases however, in most of these enzymes, the active center is either a binuclear Fe-Fe- or an Ni-Fe-complex. Although the exact... 

In line with these current developments, publishing a book dealing with the most recent achievements in this field is particularly timely. The volume is structured in chapters according to the type of metal complex. In every chapter, a brief introduction on the general chemical properties of the respective class of Fe-complexes will be given. Subsequently, representative examples for different catalytic transformations with a special emphasis on the various reaction manifolds will be presented. This structure implies that the reviews are not comprehensive but are meant to improve the understanding of the catalytic role a certain iron complex plays within the mechanism. 

Fig. 4.15), are active for ATRP of both styrene and methylmethacrylate (MMA) [46]. Polymerisation was well controlled with polydispersities ranging from 1.05 to 1.47. The rates of polymerisation 1 x 10 s ) showed the complexes to be more active than phosphine and amine ligated Fe complexes, and were said to rival Cu-based ATRP systems. It was quite recent that Cu(I) complexes of NHCs were tested as ATRP catalysts [47]. In this work, tetrahydropyrimidine-based carbenes were employed to yield mono-carbene and di-carbene complexes 42 and 43 (Fig. 4.15), which were tested for MMA polymerisation. The mono-carbene complex 42 gave relatively high polydispersities (1.4-1.8) and a low initiation efficiency (0.5), both indicative of poor catalyst control. The di-carbene complex 43 led to nncontrolled radical polymerisation, which was ascribed to the insolubility of the complex. 

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