Metals complexes with aromatics

Ferrocene, bis(cyclopentadienide)iron, was the first transition metal complex with aromatic ligands, and its discovery induced extensive research on complexes of different transition metals and different aromatic ligands. It is therefore not surprising that borinate ion complexes of this type are known. Some complexes with five-membered heterocycles were mentioned in Section 1.21.7. In this section borinate complexes are considered in greater detail because of their formal relationship to benzene. An extensive review on transition metal complexes with boron heterocycles has recently been published (80MI12100). 

Janiak, C., A critical account on 7t-7t stacking in metal complexes with aromatic nitrogen-containing ligands. J. Chem. Soc., Dalton Trans. 2000, 3885-3896. 

Either fusion with alkali metals or reaction with aUcali-metal complexes with aromatic hydrocarbons will break down most fluorocarbon systems, due to the high electron affinities of these systems. Such reactions form the basis of some methods of elemental analysis [13], the fluorine being estimated as hydrogen fluoride after ion exchange. Surface defluorination of PTFE occurs with alkali metals and using other techniques [14]. Per-fluorocycloalkanes give aromatic compounds by passage over hot iron and this provides a potential route to a variety of perfluoroaromatic systems (Chapter 9, Section IB). 

Zhao G, Lin H. Metal complexes with aromatic N-containing ligands as potential agents in cancer treatment. Curr Med Chem Anticancer Agents. 2005 5 137-147. 

A simple binding between small molecules and DNA occurs by the process of intercalation. Intercalative binding involves a noncovalent interaction that results from the insertion of the small molecules between the base pairs of the DNA helix. Intercalation commonly occurs with flat aromatic molecules that are held perpendicular to the axis of the DNA helix. Metal complexes with aromatic ligands can intercalate into DNA. ... 

Other organo-metallic structures (based on manganese in particular), based on the chemistry of -rr complexes with aromatic structures, can also be used to improve the octane number (Guibet, 1987, p. 276). 

It resembles tetracyanoethylene in that it adds reagents such as hydrogen (31), sulfurous acid (31), and tetrahydrofuran (32) to the ends of the conjugated system of carbon atoms suffers displacement of one or two cyano groups by nucleophilic reagents such as amines (33) or sodiomalononittile (34) forms TT-complexes with aromatic compounds (35) and takes an electron from iodide ion, copper, or tertiary amines to form an anion radical (35,36). The anion radical has been isolated as salts of the formula (TCNQ) where is a metal or ammonium cation, and n = 1, 1.5, or 2. Some of these salts have... 

Picric acid, in common with several other polynitrophenols, is an explosive material in its own right and is usually stored as a water-wet paste. Several dust explosions of dry material have been reported [1]. It forms salts with many metals, some of which (lead, mercury, copper or zinc) are rather sensitive to heat, friction or impact. The salts with ammonia and amines, and the molecular complexes with aromatic hydrocarbons, etc. are, in general, not so sensitive [2], Contact of picric acid with concrete floors may form the friction-sensitive calcium salt [3], Contact of molten picric acid with metallic zinc or lead forms the metal picrates which can detonate the acid. Picrates of lead, iron, zinc, nickel, copper, etc. should be considered dangerously sensitive. Dry picric acid has little effect on these metals at ambient temperature. Picric acid of sufficient purity is of the same order of stability as TNT, and is not considered unduly hazardous in regard to sensitivity [4], Details of handling and disposal procedures have been collected and summarised [5],... 

In order to put the discussion on a more quantitative basis we consider one of the more traditional and conceptually simpler methods. Obviously, when speaking about ligands one must take into account that a ligand can bear different substituents. To correlate the variation of the redox potential of a metal complex with the electronic effects played by the substituents of an aromatic ring ligand one uses the Hammett equation in its electrochemical form ... 

Phospholide ions can form metal complexes with different coordination numbers / -complexation is characteristic for their aromatic behavior. The first 7 -complex with Mn(CO)3 (7) was reported in 1976. The ring in some cases (e.g., in 7) is not strictly planar. In 7, the P atom is displaced by 0.041 A from the plane of the carbon atoms. The large number of... 

That this comparison seems to have validity (neglecting the legitimated analogy between bis-JT-allylnickel and symmetry-reduced benzene) may be atMboted to the fact that open-chain TT-systems may display some residual aromaticity (see Ref. ). Metal complexes with C3 symmetry must have three identical ligands (S) in the same state. When we change only one l and (S versus L) symmetry is reduced. The structural consequence is the change to a T- or Y-shaped moiety (see Fig. 1 in Scheme 2.5-4 and similar discussions in Refs. Within thcK arran ... 

Concerning the question of phosphole aromaticity there are some indications of 6-rr-delocalization from NMR spectroscopy and other physical methods. The formation of metal complexes with derivatives of Mn, Fe and other metals, however, gives the best chemical proof of such 6ir- delocalization but there are still some doubts arising from the considerable differences in chemical behaviour compared with pyrroles, furans and thiophenes. This once more points to the very different properties of phosphorus, compared to nitrogen in particular. Therefore the problem is still open and much work, both practical and theoretical, remains. 

In the original process using tin amides, transmetallation formed the amido intermediate. However, this synthetic method is outdated and the transfer of amides from tin to palladium will not be discussed. In the tin-free processes, reaction of palladium aryl halide complexes with amine and base generates palladium amide intermediates. One pathway for generation of the amido complex from amine and base would be reaction of the metal complex with the small concentration of amide that is present in the reaction mixtures. This pathway seems unlikely considering the two directly observed alternative pathways discussed below and the absence of benzyne and radical nucleophilic aromatic substitution products that would be generated from the reaction of alkali amide with aryl halides. 

Arylamines are commonplace. They are part of molecules with medicinally important properties, of molecules with structurally interesting properties, of materials with important electronic properties, and of transition metal complexes with catalytic activity. An aryl-nitrogen linkage is present in nitrogen heterocydes such as indoles [1, 2] and benzopyr-azoles, conjugated polymers such as polyanilines [3-9], and readily oxidizable triarylamines used in electronic applications [10-13]. The ability of aryl halides and triflates to form arylamines allows a single group to be used as a synthetic intermediate in aromatic carbon-... 

As before, the enzymatic reduction is the method of choice for the enantioselective reduction of purely aliphatic ketones and only in the case of fert-butyl methyl ketone could the bench mark of 90 % ee be crossed by the transfer hydrogenation and both other catalytic hydrogenation methods. However, substantial success in the hydrogenation of aromatic ketones by transition metal complexes with respect to the enantioselectivity and the activity (TON) strengthens the confidence that further progress is possible, enabling us to use some advantages of these nonenzymatic processes for extended application in the near future, for example in the facilitation of product isolation. 

These are halogenated adds, metallic halogenides or a mixture of both, forming complexes with aromatics, AIO —HCl, BF3—HF, etc. They act according to the following prindple ... 

Kottis and Lefebvre (322) have suggested that if polarized light is used to excite randomly oriented molecules to the triplet state, observation of the changes in the AMg = +1 ESR spectrum can reveal the correlation of the polarization properties of the excitation with the principal axis system of the triplet zero-field tensor. Such photoselection experiments have been carried out successfully by Lhotse and coworkers (323) and El-Sayed and Siegel (324) on a number of aromatic systems. Piette and collaborators (325) have studied the effect of metal complexation on the zero-field parameters and lifetimes of the phosphorescent triplet of aromatic-metal complexes with similar photoselection technique. The changes in... 

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