Covalent binding of metal complexes

Jaquet L, Kelly JM, Kirsch-De Mesmaeker A (1995) Photoadduct between tris(1,4,5,8-tetraazaphena nthrene)ruthenium(ll) and guanosine monophosphate - a model for a new covalent binding of metal complexes to DNA. J Chem Soc Chem Commun 913-914 Jay-Gerin J-P, Ferradini C (2000) A new estimate of the OFI radical yield at early times in the radiolysis of liquid water. Chem Phys Lett 317 388-391... 

Photolytic Covalent Binding of Metal Complexes to DNA Mark A. Billadeau and Harry Morrison... 

Sections 5.2 and 5.3 describe with a few examples the covalent, coordinative and ionic binding of metal complexes. This is a well-developed field. Well-characterized new polymeric systems can be obtained based on defined polymers and metal complexes. 

The hydrolysis of esters by the nickel derivative (271) provided an early example of the use of a metal-capped cyclodextrin as a catalyst (shown here as its p-nitrophenyl acetate inclusion complex) (Breslow Overman, 1970 Breslow, 1971). The synthesis of this host involves the following steps (i) covalent binding of the pyridine dicarboxylic acid moiety to cyclodextrin, (ii) coordination of Ni(n) to this species, and (iii)... 

The covalent binding of a metal complex to a solid support is the most commonly applied technique of functionalizing a microporous or mesoporous material. In essence, this technique can be further categorized into two subsections (1) grafting, this is the direct attachment of a metal complex to the silica framework of the material and (2) tethering, whereby a spacer ( tether ) is used between the wall of the material and the metal complex. 

The metallointercalation reagents are a class of heavy metal derivatives that bind to double-stranded polynucleotides by inserting between adjacent base pairs in the helix.1 2 Prototype members of this class of intercalators are (2,2 6, 2"-terpyridine)(thiolato)platinum(II) complexes.3 These may be synthesized from chloro(2,2 6, 2"- terpyridine)platinum(II), which can both intercalate and bind covalently by losing chloride ion. Covalent binding of the thiolato complexes is much slower owing to the more inert character of the Pt—S bond. Metallointercalation reagents also have the potential to bind to proteins that have natural receptor sites for nucleic acid bases. They may therefore also be used to provide isomorphous heavy atom derivatives for X-ray analysis. 

Covalent binding of ligands to supports is by far the most frequently used strategy for the heterogenization of metal complexes and, in general, the successful catalytic systems are sooner or later immobilized by this method. Covalent binding can be effected either by copolymerization or by grafting. 

There have been many reports that described protein composites containing metal complexes [1-3, 5, 6], Three different approaches for the incorporation of synthetic metal complexes into protein cavities have been reported (i) modification of natural snbstrates, (ii) covalent anchoring, and (iii) non-covalent insertion. For example, Whiteside et al. constructed artificial metaUoenzymes by the conjugation of a Rh diphosphine complex with biotin, which strongly binds to avidin [8], Ward et al. have improved this method to increase the reaction activities [25]. They optimized the reaction conditions by screening the structures of metal complexes and protein environments. Finally, optimized composites catalyzed asymmetric hydrogenation with np to 97% ee (Fig. 2a) [2, 3, 26],... 

---