Diimine Iron Complexes

In recent studies on hydrogenation catalyzed by soluble iron-diimine complexes, Chirik and coworkers noted that the major deactivation pathway of these complexes occurs via formation of tj6-arene complexes [54]. 

There is a brief but eomprehensively referenced section on iron in a review of homoleptie 2,2-bipyridyl eomplexes " iron-terpy (3 pages) and iron-quaterpy (1/2 page) complexes have also been briefly reviewed." Absorption spectra and photochemistry of apprcmriate iron diimine complexes are ineluded in a text on polypyridyl and porphyrin complexes." A review of the applieation of ehiral 2,2 -bipyridines, 1,10-phenanthrolines, and 2,2 6, 2"-terpyridines in homogeneous eatalysis eontains a little material on iron complexes of such ligands." ... 

Activation volumes for aquation of Schiff base complexes [Fe(C5H4NCH=NHR)3] + (R = Me, Et, Pr , Bu ) in 0.1 M aqueous HCl are between - -11 cm mol and - -14cm mol v and thus within the range established earlier " for (substituted) tris-l,10-phenanthroline-iron(II) complexes. These positive values are consistent with dissociative activation, as are those for dissociation of [Fe(5Brphen)3] + and of [Fe(5N02phen)3] " " in the presence of edta. AF and values for aquation of [Fe(5Brphen)3] have the subject of isochoric analysis. " Medium effects on activation volumes have been reviewed for iron-diimine complexes in binary aqueous solvent mixtures. 

Okamoto and coworkers recently described the iron-catalyzed cyclotrimerization of alkynes utilizing a low-valent iron-diimine complex that was generated in situ upon reduction with zinc dust (Scheme 9.34) [92]. 

There are very few examples of asymmetric synthesis using optically pure ions as chiral-inducing agents for the control of the configuration at the metal center. Chiral anions for such an apphcation have recently been reviewed by Lacour [19]. For example, the chiral enantiomerically pure Trisphat anion was successfully used for the stereoselective synthesis of tris-diimine-Fe(ll) complex, made configurationally stable because of the presence of a tetradentate bis(l,10-phenanthroline) ligand (Fig. 9) [29]. Excellent diastereoselectivity (>20 1) was demonstrated as a consequence of the preferred homochiral association of the anion and the iron(ll) complex and evidence for a thermodynamic control of the selectivity was obtained. The two diastereoisomers can be efficiently separated by ion-pair chromatography on silica gel plates with excellent yields. 

Cyanide-bridged complexes involving iron-diimine-cyanide complexes are discussed in Section 5.4.3.5.8. 

Bithiazole, 4,4 -btz = (97), is not a diimine its iron(II) complex [Fe(4,4 -btz)3] is only weakly colored but its magnetic properties and Fe—N bond distances 1.970-1.973A suggest that the ligand field effect of 4,4 -btz is not enormously less than that of bipy. ... 

Transfer chemical potentials for the low-spin amine-diimine complexes [Fe(tsba)2] " with tsba = (8 were estimated from the solubilities of their perchlorate salts, in methanol-water mixtures.Solubility and transfer chemical potential data are also available for [Fe(Me2bsb)3] " " in several nonaqueous solvents. One of the main purposes in determining transfer chemical potentials for these iron(II)-diimine complexes is to enable dissection of reactivity trends into initial state and transition state components for base hydrolysis (see next section) in binary aqueous solvent mixtures. Systems for which this has been achieved are indicated in Table 8. 

Table 8 Solvation of iron(II)-diimine complexes in binary aqueous solvent mixtures. ... 

Activation volumes for dissociation, base hydrolysis, cyanide attack, and peroxodisulfate oxidation (see following pages) of iron(II)-diimine complexes are collected together in Table 9. 

Table 9 Activation volumes (cm mol ) for reactions of iron(II)-diimine complexes, in aqueous solution at...

Figure 2 Diagrammatic summary of selected structural, substituent, and solvent effects on rate constants (kj, at 298 K) for base hydrolysis of low spin iron(II)-diimine complexes. Ligand abbreviations not appearing in the list at the end of this chapter are apmi = (73) with = Me BOH cage = (78) with X = OH ...

Fe(gmi)3] in glycol-water and a range of other binary aqueous solvent mixtures. These results, along with further results for AV for base hydrolysis of [Fe(phen)3] " and of [Fe(bipy)3] " in alcohol-water mixtures, have permitted the construction of a scheme combiniim solvent and ligand effects on AF for base hydrolysis of a range of diimine-iron(II) complexes. ... 

Substitution reactions of hexadentate diimine complexes of iron(II) are generally slow, thanks to the combination of the strongly binding diimine groups and the chelate effect, even when the ligand contains only two diimine units of the less strongly bonding py—CH=N— type k2(OH)... 

The iron(II) complex of the Schiff base-diimine (121) is mentioned briefly in a review more concerned with Cu" "-diimine complexes leading to helicates and catenanes—but which is also concerned with moving from tetrahedral Cu+ to octahedral metal centers as templates. 

Piezochromism and thermochromism of diimine-cyanide-iron(II) and -iron(III) complexes (diimine = bipy or phen), piezochromism and solvatochromism of dicyano-, tricyano-, and tetracyano- diimine- (terimine-) ironlll) complexes, and piezochromism of [Fe(bipy)2(CN)2] in 90% Pr OH have been documented. ... 

The solvatochromic behavior of the closely related iron(0) complexes Fe(CO)3(diimine) is mentioned under lower oxidation states (Section 5.4.3.5.6). 

Reaction kinetics and mechanisms for oxidation of [Fe(diimine)2(CN)2], [Fe(diimine)(CN)4] (diimine = bipy or phen) (and indeed [Fe(CN)6] ) by peroxoanions such as (S20g, HSOs", P20g ) have been reviewed. Reactivity trends have been established, and initial state— transition state analyses carried out, for peroxodisulfate oxidation of [Fe(bipy)2(CN)2], [Fe(bipy)(CN)4] , and [Fe(Me2bsb)(CN)4] in DMSO—water mixtures. Whereas in base hydrolysis of iron(II)-diimine complexes reactivity trends in binary aqueous solvent mixtures are generally determined by hydroxide solvation, in these peroxodisulfate oxidations solvation changes for both partners affect the observed pattern. ... 

The ferrocene-linked bis-bipy and bis-phen ligands (181) and (182) form very stable iron(II) complexes in which the ligands are bonded to the metal through two carbonyl oxygens in addition to the two diimine groups." ... 

The synthesis of metal-coordinated 1-azirines and the reactions of azirines induced by metals have opened a new area in the chemistry of this small ring heterocycle. Many of the reactions encountered bear resemblance to previously discussed thermally and photo-chemically induced reactions of 1-azirines. The reaction of a series of diiron enneacarbonyls in benzene results in coupling and insertion to give diimine complexes and ureadiiron complexes as well as pyrroles and ketones (76CC191). A mechanism for the formation of these products which involves initial 1,3-bond cleavage and generation of a nitrene-iron carbonyl complex as an intermediate was proposed. 

Iron(III) complexes are generally more labile than analogous complexes of both ruthenium(III) and osmium(III), and this also holds for the diimine complexes discussed here. In acidic and neutral solution,... 

Fig. 5. Free energy correlations between the rates of reduction of tris diimine)iron(lII) complexes [cf. Eq. (2) ] and the acid dissociation constants of the di- and monoprotonated free ligands. The lines are drawn with slopes of 1.00. The data are from McBryde (11) and from Table II.

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