Other Arene Complexes

5 Other Arene Complexes.- The new n -benzene ligand has been 

Greenfield and M. Ker iting, J.Chem.Soc., Chem. Conmun.. 

Winter, G. Huttner, M. Gottlieb and I, Jibril, J.Organomet.Chem.. 

Werner, L.H. Hofmann, R. Peser and W. Paul, J.Orqanomet.Chem., 1985, 

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The U ring distances are short relative to other ) -arene complexes, ranging from 2.503(9) to 2.660(8) A. In addition, there is a slight distortion in the bound toluene hgand the average C-C distance increases by approximately 0.04A compared to that found in free toluene. Density functional calculations carried out on the molecule suggest that four... 

Dibenzenechromium, which forms dark brown crystals, is much more sensitive to air than is ferrocene, with which it is isoelectronic it does not survive the reaction conditions of aromatic substitution. X-ray and electron-diffraction measurements on dibenzenechromium and other arene complexes show that the carbon—carbon bond lengths are equivalent.16 As with the A5-C5H5 compounds, a variety of complexes with only one arene ring have been prepared, for example,... 

We are currently extending these studies to other arene complexes of Cr" in order to address some of the more peculiar aspects such as the following questions ... 

This method may be utilized for the preparation of most arene sandwich compounds as well as for many other arene complexes. However, it cannot be used for manganese arene derivatives. 

Elegant evidence that free electrons can be transferred from an organic donor to a diazonium ion was found by Becker et al. (1975, 1977a see also Becker, 1978). These authors observed that diazonium salts quench the fluorescence of pyrene (and other arenes) at a rate k = 2.5 x 1010 m-1 s-1. The pyrene radical cation and the aryldiazenyl radical would appear to be the likely products of electron transfer. However, pyrene is a weak nucleophile the concentration of its covalent product with the diazonium ion is estimated to lie below 0.019o at equilibrium. If electron transfer were to proceed via this proposed intermediate present in such a low concentration, then the measured rate constant could not be so large. Nevertheless, dynamic fluorescence quenching in the excited state of the electron donor-acceptor complex preferred at equilibrium would fit the facts. Evidence supporting a diffusion-controlled electron transfer (k = 1.8 x 1010 to 2.5 X 1010 s-1) was provided by pulse radiolysis. 

Several other versions of these catalysts have been developed. Arene complexes of monotosyl-l,2-diphenylethylenediamine ruthenium chloride give good results with a,(3-ynones.55 The active catalysts are generated by KOH. These catalysts also function by hydrogen transfer, with isopropanol serving as the hydrogen source. Entries 6 to 8 in Scheme 5.3 are examples. 

Other [AuCIL] complexes with monophosphines are those derived of o-carborane (427),2506 pyr-anoside group (428),2507 a-dimethylamino(3)ferrocenophan-2-yl,2508 calix[4]arene derived phosphites,25 or aminoxyl radical-substituted phosphines (429),2510 for which ferromagnetic interactions have been observed. 

In addition to [Hg( -toluene)2-(GaCI/ )2],168 other mercury-arene complexes of general formula [I Ig( /2-arene)2-(AlCUy have been prepared.169 These include the bis(toluene), bis(o-xylene), and bis(l,2,3-trimethylbenzene) complexes 159, 160, and 161, respectively, whose structures have all been determined (Figure 8). While the arene in 159 and 161 is coordinated in an asymmetrical -fashion, the /2-1,2,3-trim ethylbenzene ligands of 160 form two nearly equal Hg-C bonds of 2.45 and 2.46 A. DFT calculations show that the Hg-arene interactions are mostly ionic. 

We have recently extended our interest to the analogous halfsandwich osmium-arene complexes and are exploring the chemical and biological properties of [Os(r 6-arene)(XY)Z]ra 1 complexes (Fig. 25) (105). Both the aqueous chemistry and the biological activity of osmium complexes have been little studied. Third-row transition metals are usually considered to be more inert than those of the first and second rows. Similar to the five orders of magnitude decrease in substitution rates of Pt(II) complexes compared to Pd(II), the [Os(ri6-arene)(L)X]"+ complexes were expected to display rather different kinetics than their Ru(II)-arene analogs. A few other reports on the anticancer activity of osmium-arene complexes have also appeared recently (106-108). 

Species functionalized at boron, such as 50-53, have also been prepared from the corresponding MC2B4 closo clusters via the removal of the apex BH unit (decapitation) with I M Kl)A.54 57 The same approach has been employed to link CoC2B3 units to benzene or other arenes 5 As shown in the following subsection, di- and trinuclear complexes such as 53 and 54 are easily converted to multi-triple-decker sandwich systems. 

Bis(Tj6-jV,-/V-dimethylaniline)molybdenum has been prepared in good yield by cocondensation of molybdenum atoms with a fifty-fold excess of Af,Af-dimethyl-aniline vapor on a liquid nitrogen cooled surface. This method has been extended to the synthesis of other molybdenum arene complexes and is at present the only synthetic route to such compounds. 

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