Terpyridine, complexing with

Breul AM, Schafer J, Friebe C, Schliitter F, Paulus RM, Festag G, Hager MD, Winter A, Dietzek B, Popp J, Schubert US (2012) Synthesis and characterization of poly(methyl methacrylate) backbone polymers containing side-chain pendant ruthenium(II) bis-terpyridine complexes with an elongated ctmjugated system. Macromol Chem Phys 213 808-819... 

Construction of one-dimensional multicomponent molecular arrays, transition metal complexes with terpyridines and/or porphyrins as ligands 98EJI1. 

Vectorial transfer of electronic energy in rod-like ruthenium-osmium complexes with bis-2,2, 2"-terpyridine ligands 97CC333. 

To mimic the square-pyramidal coordination of iron bleomycin, a series of iron (Il)complexes with pyridine-containing macrocycles 4 was synthesized and used for the epoxidation of alkenes with H2O2 (Scheme 4) [35]. These macrocycles bear an aminopropyl pendant arm and in presence of poorly coordinating acids like triflic acid a reversible dissociation of the arm is possible and the catalytic active species is formed. These complexes perform well in alkene epoxidations (66-89% yield with 90-98% selectivity in 5 min at room temperature). Furthermore, recyclable terpyridines 5 lead to highly active Fe -complexes, which show good to excellent results (up to 96% yield) for the epoxidation with oxone at room temperature (Scheme 4) [36]. 

Si. rra(pentafluorophenyl)boron was found to be an efficient, air-stable, and water-tolerant Lewis-acid catalyst for the allylation reaction of allylsilanes with aldehydes.167 Sc(OTf)3-catalyzed allylations of hydrates of a-keto aldehydes, glyoxylates and activated aromatic aldehydes with allyltrimethylsilane in H2O-CH3CN were examined. a-Keto and a-ester homoallylic alcohols and aromatic homoallylic alcohols were obtained in good to excellent yields.168 Allylation reactions of carbonyl compounds such as aldehydes and reactive ketones using allyltrimethoxysilane in aqueous media proceeded smoothly in the presence of 5 mol% of a CdF2-terpyridine complex (Eq. 8.71).169... 

A general strategy developed for the synthesis of supramolecular block copolymers involves the preparation of macromolecular chains end-capped with a 2,2 6/,2//-terpyridine ligand which can be selectively complexed with RUCI3. Under these conditions only the mono-complex between the ter-pyridine group and Ru(III) is formed. Subsequent reaction with another 2,2 6/,2"-terpyridine terminated polymer under reductive conditions for the transformation of Ru(III) to Ru(II) leads to the formation of supramolecular block copolymers. Using this methodology the copolymer with PEO and PS blocks was prepared (Scheme 42) [ 107]. 

Substituted terpyridine, 4,4, 4"-tris(5-nonyl)-2,2 <5, 2"-terpyridine (tNtpy), is a planar tridentate ligand that was successfully used in homogeneous ATRP of methyl acrylate and styrene [79]. Polymerization of both monomers was controlled and the resulting polymers had relatively low polydispersities (MJMn < 1.2). Similarly to PMDETA, the typical ligand to copper halide ratio used in the polymerization was 1 1. Terpyridine and its derivatives are expected to form tetra-coordinated complexes with copper in which the fourth coordination sphere is occupied by a monodentate ligand (Br-, Cl , solvent, monomer, etc.). Although,... 

Several approaches have been undertaken to construct redox active polymermodified electrodes containing such rhodium complexes as mediators. Beley [70] and Cosnier [71] used the electropolymerization of pyrrole-linked rhodium complexes for their fixation at the electrode surface. An effective system for the formation of 1,4-NADH from NAD+ applied a poly-Rh(terpy-py)2 + (terpy = terpyridine py = pyrrole) modified reticulated vitreous carbon electrode [70]. In the presence of liver alcohol dehydrogenase as production enzyme, cyclohexanone was transformed to cyclohexanol with a turnover number of 113 in 31 h. However, the current efficiency was rather small. The films which are obtained by electropolymerization of the pyrrole-linked rhodium complexes do not swell. Therefore, the reaction between the substrate, for example NAD+, and the reduced redox catalyst mostly takes place at the film/solution interface. To obtain a water-swellable film, which allows the easy penetration of the substrate into the film and thus renders the reaction layer larger, we used a different approach. Water-soluble copolymers of substituted vinylbipyridine rhodium complexes with N-vinylpyrrolidone, like 11 and 12, were synthesized chemically and then fixed to the surface of a graphite electrode by /-irradiation. The polymer films obtained swell very well in aqueous... 

Terpyridine ligands are known to form mono- and Ins-complexes with a wide variety of transition metal ions [321]. The stability constants and the kinetics of formation of these different complexes strongly depend on the nature of the used metal ions [322], In this respect, Rum is known to form a very stable mono-complex with one terpyridine ligand, while Ru11 only forms a stable bzs-complex with two terpyridine ligands [323]. 

Terpyridine moieties have been introduced as a terminal unit of macromolecules. In a subsequent procedure the two-step self-assembly process based on Rum/Run chemistry was used for polymers end-capped with the 2,2/ 6/,2 -terpyridine ligand. More precisely, the terpyridine-functionalized polymers were complexed with RUCI3 to selectively form a mono-complex. In a further step, this mono-complex was reacted under reducing conditions with other uncomplexed 2,2/ 6/,2/-terpyridine-terminated polymer blocks in order to form an asymmetrical AB ruthenium(II) frzs-complex. 

Let us now consider the N6-coordinated octahedral vanadium complexes with the polypyridine ligands 1,10-phenantroline (phen), 2,2/-bipyridine (bipy) and 2,2/ 6,2//-terpyridine (terpy), Scheme 3. 

Table 6 compiles the electrode potentials of the chromium complexes with phenantroline, bipyridine and terpyridine ligands, respectively25-27. 

In these cases, there is the expected tetragonal distortion due to the Jahn-Teller effect in addition to the often mentioned octahedral distortion associated with polypyridine complexes. For the terpyridine complex there is the usual difference between the distances separating the metal and nitrogen atom of the central pyridine and that of the metal and the nitrogen atom of the peripheral pyridines. 

Pentadentate 2,2 6, 2"-terpyridine, 30 107 Pentadiene complexes with iron, 12 255-257 with rhodium, 12 295 with silver, 12 340 Pentadienyl complexes with group VIB metals, 12 224, 225 with group VIIB metals, 12 240 JV,Af,/V,lV",N"-Pentaethyldiethylenetriamine, 42 76... 

The series of Zn(II) complexes with 1-amidino-3-aryl-substituted-thioureas [121], acetamidomalondihydroxymate [122], benzilbisthiosemicarbazone [123], novel fluorene-substituted terpyridine [124], per-fluoroalkoxy-substituted phthalocyanine [125], and 3-carboxylacetonehydroxamic acid [126] were synthesized. The behavior of these complexes was investigated by spectroscopic and electrochemical methods. 

N3C9H21, N,N N"-Trimethyl-1,4,7-triazacyclo-nonane, Me3tacn, complexes with chromium(III), 34 151-154 N3C15H11, terpy, 2,2 6 2 -Terpyridine,... 

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