Rhenium complexes macrocycles

Macrocyclic receptors made up of two, four or six zinc porphyrins covalently connected have been used as hosts for di- and tetrapyridyl porphyrins, and the association constants are in the range 105-106 M-1, reflecting the cooperative multipoint interactions (84-86). These host-guest complexes have well-defined structures, like Lindsey s wheel and spoke architecture (70, Fig. 27a), and have been used to study energy and electron transfer between the chromophores. A similar host-guest complex (71, Fig. 27b) was reported by Slone and Hupp (87), but in this case the host was itself a supramolecular structure. Four 5,15-dipyridyl zinc porphyrins coordinated to four rhenium complexes form the walls of a macrocyclic molecular square. This host binds meso-tetrapyridyl and 5,15-dipyridyl porphyrins with association constants of 4 x 107 M-1 and 3 x 106 M-1 respectively. 

The present volume is the fourth in the series and covers the topics lithium in biology, the structure and function of ceruloplasmin, rhenium complexes in nuclear medicine, the anti-HIV activity of macrocyclic polyamines and their metal complexes, platinum anticancer dmgs, and functional model complexes for dinuclear phosphoesterase enzymes. The production of this volume has been overshadowed by a very sad event—the passing away of the senior editor, Professor Robert W. Hay. It was he who conceived the idea of producing this series and who more than anyone else has been responsible for its continuation. A tribute by one of his many friends, Dr. David Richens, is included in this Volume. 

The prototypical photochemical system for CO2 reduction contains a photosensitizer (or photocatalyst) to capture the photon energy, an electron relay catalyst (that might be the same species as the photosensitizer) to couple the photon energy to the chemical reduction, an oxidizable species to complete the redox cycle and CO2 as the substrate. Figure 1 shows a cartoon of the photochemical CO2 reduction system. An effective photocatalyst must absorb a significant part of the solar spectrum, have a long-lived excited state and promote the activation of small molecules. Both organic dyes and transition metal complexes have been used as photocatalysts for CO2 reduction. In this chapter, CO2 reduction systems mediated by cobalt and nickel macrocycles and rhenium complexes will be discussed. 

The approaches to heterometaUic systems outlined above all rely upon coordination chemistry, whether to a metal ion or a nanoparticle surface. Supramolecular interactions can also play a role in assembling heterometaUic systems. For instance, Sambrook et al. prepared a pseudo-rotaxane (18) templated around a chloride ion (Fig. 9) in which lanthanide ions are bound to the thread while a luminescent rhenium complex is bound to the macrocycle component [49]. Thus there is no direct link between the donor chromophore and the lanthanide ion, and Dexter exchange is not viable in the absence of bonds enforcing Forster energy transfer. This extreme of behaviour helps to rationalize the behaviour of more conventionaUy... 

Larger rhenium complexes are also the subject of a number of publications. Reaction of an excess of thietane with the thietane complex fRe3(CX))jQ(p-H)3(p-cyclo-SCH2CH2CH2)] affords a number of ring-opening oligomerisation products from which sulfur containing macrocycles such as 12-S-4, 16-S-4 and 24-S-6 can be eliminated upon addition of pyridine . Addition of... 

Other systems for electrochemical CO2 reduction utilize transition metal complexes of nitrogen-containing (nickel and cobalt) macrocycles (including porphyrins and phthalocyanines) and (ruthenium, cobalt, and rhenium) complexes of 2,2 -bipyridine. ... 

Baker RJ, Edwards PG, Gracia-Mora J et al (2002) Manganese and rhenium triphosphcnus macrocycle complexes and reaetions with alkenes. J Chem Soc Dalton Trans 3985-3992... 

Metal-Directed Macrocyclic Complexes Incorporating Diimine Rhenium Tricarbonyl Moieties... 

The synthesis and X-ray crystal structure of the macrocyclic bisphosphine oxide manganese complex (75) have been reported. A stable P-bonded phosphinidene oxide complex (77) of rhenium (1) has been prepared from (76) by nitrogen replacement with C-tertiarybutylphosphaalkyne followed by hydrolysis. 1 X-Ray crystallography was used to determine the structure of (77). What is reported to be the first complex (78) with a PO ligand has been prepared. 2 The molecular structure of (78), determined by X-ray crystallography, shows an exceptionally short PP distance. 

The polymerization is effected by a complex catalyst system. One such system has three main components. The first of these is typically a halide or acetyl-acetonate of tungsten, molybdenum, tantalum or rhenium the second a trialkyl aluminium or dialkyl aluminium chloride and the third component an activator such as epichlorhydrin or 2-chloroethanol. The polymerization may be carried out in bulk in the temperature range -50 to 0°C. The molecular weight may be regulated by the addition of small amounts of butene. The final polymer molecules are not necessarily macrocyclic in nature due to bond scission. This explanation has been shown to be consistent with the existence of vinyl end-groups even where no chain terminating non-cyclic mono-olefins have been specificaUy added. 

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