Diimine Metal Complexes

An article describing some reactions of metal diimine complexes. 

Although ferryl intermediates of horseradish peroxidase and microperoxidase-8 have been produced in reactions with photogenerated [Ru(bpy)3]3+ [5], analogous experiments with P450s were unsuccessful, presumably due to the inefficiency of electron transfer from the buried heme active site through the protein backbone [6]. Photoactive molecular wires (sometimes referred to as metal-diimine wires, sensitizer-tethered substrates, or electron tunneling wires) were developed to circumvent this problem by providing a direct ET pathway between [Ru(bpy)3]3+ and the heme. These molecular wires, which combine the excellent photophysical properties of metal-diimine complexes... 

The 3D frameworks can be obtained from metaloxalate metaUohgands by employing metal-diimine complexes [M(bpy)3] as the counterions. These frameworks have typical formulas of M" " [M (ox)3] and [M " (ox)3] ... 

It is generally agreed that the intense absorption bands in the near UV spectra of metal diimine complexes, first recorded by Yamasaki 61), arise from n n transitions of the ligands slightly perturbed by the... 

Several combinatorial approaches to the discovery of transition metal based catalysts for olefin polymerization have been described. In one study Brookhart-type polymer-bound Ni- and Pd-(l,2-diimine) complexes were prepared and used in ethylene polymerization (Scheme 3).60,61 A resin-bound diketone was condensed with 48 commercially available aminoarenes having different steric properties. The library was then split into 48 nickel and 48 palladium complexes by reaction with [NiBr2(dme)] and [PdClMe(COD)], respectively, all 96 pre-catalysts being spatially addressable. 

One of the most defining characteristics of the late metal a-diimine polymerization systems is the uniquely branched polyolefins that they afford. This arises from facile p-hydride elimination that late transition metal alkyl complexes undergo. The characteristics of the isomerization process have been the subject of much investigation, particularly with the more easily studied Pd(II) a-diimine system. The process is initiated by P-hydride elimination from the unsaturated alkyl agostic complex 1.17, followed by hydride reinsertion into olefin hydride intermediate 1.18 in a non-regioselective manner (Scheme 5). In doing so, the metal center may migrate... 

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. 

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. 

Various methods to prepare tris(ar-diimine) complexes of many metals in low oxidation states have been devised, mainly by Herzog and co-workers.32 Those used for chromium complexes are illustrated in Schemes 5 and 6. Chromium(II) salts, anhydrous or hydrated, are the commonest starting materials. To these are added stoichiometric amounts of the diimine,... 

The mechanism depicted in Scheme 2 involves two main steps. Rupture of the first metal-nitrogen bond accompanied by coordination of a water ligand at the metal center is followed by reversible deprotonation and intramolecular reduction of the metal center. Under the experimental conditions wherein the concentration of base is much larger than the concentration of tris(diimine) complex, and, applying the steady-state approximation to the concentration of the intermediate species with the monodentate diimine ligand, Eq. (6) can be derived as... 

The oxygenation of the fi-diimine complex to give compound (66) (Scheme 71) could be a more general process as both the diheteroarylmethanes (69) and (70) undergo metal-catalyzed oxygenation to the related products (71) and (72) respectively.225-226... 

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. 

In similar but more complicated processes, chelated a-diimines can be formed by reaction of ruthenium(III) and osmium(III) ammine complexes with biacetyl however, reduction of the metal also occurs (Scheme 49).220 A 0-diimine complex is obtained when acetylacetone undergoes reaction with hexaammineplatinum(TV) ions in basic solution (equation 39).220... 

As mentioned above, reactions of this type have been widely used in the synthesis of macrocyclic ligands. Indeed, some of the earliest examples of templated ligand synthesis involve thiolate alkylations. Many of the most important uses of metal thiolate complexes in these syntheses utilise the reduced nucleophilicity of a co-ordinated thiolate ligand. The lower reactivity results in increased selectivity and more controllable reactions. This is exemplified in the formation of an A -donor ligand by the condensation of biacetyl with the nickel(n) complex of 2-aminoethanethiol (Fig. 5-78). The electrophilic carbonyl reacts specifically with the co-ordinated amine, to give a complex of a new diimine ligand. The beauty of this reaction is that the free ligand cannot be prepared in a metal-free reac-... 

Presumably, the oxidation of the iron(n) diimine complex derived from glyoxal and methylamine (encountered previously) by cerium(iv) occurs by a related mechanism (Fig. 9-37). This also provides an interesting example of the metal ion stabilising a particular tautomer of a ligand. The free ligand would be expected to exist as the amide tautomer 9.22. 

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