2,2 -Bipyridine reduction

An indication that the intramolecular redox equilibrium between the first polypyridine reduction and the more negative vinyl ligand reduction is responsible for the radical initiation and subsequent film formation reaction of Ru(bpy)2(vinyl-ligand)22+ complexes is demonstrated in Figure 7. From the data for the various Ru(bpy)2(4 -X-stilb)2 + complexes in Table 2 it is seen that the first bipyridine reductions (Ej red.l)) all occur at approximately the same potential (-l.22jj3.03V). Thus, a disproportionation equilibrium will exist (eq. 13) which depends upon the reduction potential of the coordinated vinyl ligand. 

The UV-visible absorption spectrum of Ru(2,2 -bipyridine)3 maximum at about 450 nm, from which the energy in volts for process XI-39 may be estimated. The standard reduction potential for the R" /R couple is about 1.26 V at 25°C. Estimate from this information (and standard reduction potentials) the potential in volts for processes XI-40 and XI-41. Repeat the calculation for alkaline solutions. 

In analogy to the situation for bipyridine, the blue tris(l,10-phenanthroline)iron(3+) ion [1347949-7], [Fe(phen)2], must be obtained by oxidation of the corresponding iron(II) ion. [Fe(phen)2] has an absorption maximum at 590 nm, an absorptivity of 600 (Mem), and a formation constant of 10 . In solutions of pH > 4, this species is reduced to the iron(II) complex. The reduction is instantaneous in alkaline solution. At pH < 2, protons compete with iron(III) for the phenanthroline nitrogens and coordination is incomplete. [Fe(phen)2] is used most often in solution as an oxidant, but the trichloride [40273-22-1] and the triperchlorate monohydrate [20774-81-6] salts have been prepared. 

Ascorbic acid, for example, is oxidized to dehydroascorbic acid with reduction of the iron(III) ions. The Fe(II) ions so produced react with 2,2 -bipyridine with formation of a colored complex. 

Homolytic aromatic substitution often requires high temperatures, high concentrations of initiator, long reaction times and typically occurs in moderate yields.Such reactions are often conducted under reducing conditions with (TMSlsSiH, even though the reactions are not reductions and often finish with oxidative rearomatization. Reaction (68) shows an example where a solution containing silane (2 equiv) and AIBN (2 equiv) is slowly added (8h) in heated pyridine containing 2-bromopyridine (1 equiv) The synthesis of 2,3 -bipyridine 75 presumably occurs via the formation of cyclohexadienyl radicals 74 and its rearomatization by disproportionation with the alkyl radical from AIBN. ... 

Maikov et al. [37] prepared a series of C2-symmetric bipyridine-type ligands, the chiral moieties arising from the isoprenoid chiral pool (/3-pinene, 3-carene, 2-carene, or a-pinene, for example). Some representative examples are drawn in Scheme 16 (see 25, 26, 27) and were used as copper ligands of a copper(I) species obtained by an in-situ reduction of Cu(OTf )2 with phenyl-hydrazine. The use of the resulting catalysts in enantioselective cyclopropana-tion proceeded with up to 76% ee (for ligand 27) and high diastereoselectivity (up to 99 1). 

The reduction of Co(lll) by Fe(II) in perchloric acid solution proceeds at a rate which is just accessible to conventional spectrophotometric measurements. At 2 °C in 1 M acid with [Co(IlI)] = [Fe(II)] 5 x 10 M the half-life is of the order of 4 sec. Kinetic data were obtained by sampling the reactant solution for unreacted Fe(Il) at various times. To achieve this, aliquots of the reaction mixture were run into a quenching solution made up of ammoniacal 2,2 -bipyridine, and the absorbance of the Fe(bipy)3 complex measured at 522 m/i. Absorbancies of Fe(III) and Co(lll) hydroxides and Co(bipy)3 are negligible at this wavelength. With the reactant concentrations equal, plots of l/[Fe(Il)] versus time are accurately linear (over a sixty-fold range of concentrations), showing the reaction to be second order, viz. 

Ru 2,2 -bipyridine complexes can form a large number of colored compounds upon successive reduction, with the formal Ru oxidation state from +2 to -4. In the case of highly reduced complexes, proper representation of the electrochromic reaction is actually the reduction of the hgand, not that of the metal center. 

The reduction of [Pt(bipy)2]2+ in water by metallic iron or at a platinum electrode gives monomeric [Pt(bipy)2]N03-2I I20 that forms as black-green needles. 25The needles have a relatively high electrical conductivity and a Pt - Pt separation of 3.563(1) A.125 In contrast, reduction in aprotic solvents such as DMF or DMSO results in the formation of dimeric [Pt2(bipy)2(/x-bipy)]21 (bipy = 2,2 -bipyridine) with a Pt- -Pt separation of 2.527,2(5) A.126... 

Crystallography has shown that the product of the reaction of [TcNBr4] With 2,2 -bipyridine in ethanol is cA-[TcvNBr(bpy )2] 2 [Ten Br4], This remarkable and unprecedented reaction involves loss of a nitrido ligand and reduction of TeVI to Tc11 under mild conditions to yield the previously unknown [TcBr4]2. With methanol as the solvent the product is [9]BPh4 [56,57],... 

Re(bpy)(CO)3Cl-modified electrodes has not yet been explained. However, from the cyclic voltammograms of fac-Re(bpy)(CO)3Cl (Fig. 14) and from the intermediate complexes formed by electrolysis in acetonitrile in the presence and absence of C02, two different electrocatalytic pathways (Fig. 15) were suggested144 initial one-electron reduction of the catalyst at ca. -1.5 V versus SCE followed by the reduction of C02 to give CO and C03, and initial two-electron reduction of the catalyst at ca. -1.8 V to give CO with no C03. The electrochemistry of [Re(CO)3(dmbpy)Cl] (dmbpy = 4,4 -dimethyl-2,2 -bipyridine) was investigated145 to obtain mechanistic information on C02 reduction, and the catalytic reac-... 

Later, an improved system for C02 photofixation was reported by the same authors.164 The new system consisted of 6.5 x 1(T5 M tris(2,2 -bipyridine)ruthenium(II), Ru(bpy)3, as the photosensitive electron donor, methyl viologen (MV2+, 20 mM) as the electron acceptor, and triethanolamine (TEOA, 0.6 M) as a sacrificial electron donor in a C02-saturated aqueous solution (Fig. 18). Under irradiation with a 300-W high-pressure Hg lamp with a CuS04 chemical filter (A > 320 nm), formic acid, which was detected by isotachophoresis, was produced in quantum yields of ca. 0.01%. Recently, however, Kase et al.165 have repeated this experiment using a 13C02 tracer and have claimed that the formic acid obtained was produced not by C02 reduction but rather by oxidative cleavage of TEOA. 

Alkylnickel amido complexes ligated by bipyridine have been prepared that undergo reductive elimination of V-alkyl amines (Equation (54)).207,208 Unlike the phosphine-ligated palladium arylamides, these complexes underwent reductive elimination only after oxidation to nickel(III). Thermally induced reductive elimination of alkylamines from phosphine-ligated nickel complexes appears to occur after consumption of phosphine by arylazides 209... 

Rhin(bpy)3]3+ and its derivatives are able to reduce selectively NAD+ to 1,4-NADH in aqueous buffer.48-50 It is likely that a rhodium-hydride intermediate, e.g., [Rhni(bpy)2(H20)(H)]2+, acts as a hydride transfer agent in this catalytic process. This system has been coupled internally to the enzymatic reduction of carbonyl compounds using an alcohol dehydrogenase (HLADH) as an NADH-dependent enzyme (Scheme 4). The [Rhin(bpy)3]3+ derivative containing 2,2 -bipyridine-5-sulfonic acid as ligand gave the best results in terms of turnover number (46 turnovers for the metal catalyst, 101 for the cofactor), but was handicapped by slow reaction kinetics, with a maximum of five turnovers per day.50... 

The same group has also shown that mono- or dinuclear trisbipyridine-like complexes containing the ligand 2,2 -bis(l-methyl-benzimidazol-2-yl)-4,4 -bipyridine instead of unsubstituted 2,2 -bipyridine catalyze the reduction of C02 to oxalate (C2042-) in anhydrous MeCN at — 1.65 V and —1.55 V, respectively (vs. Ag AgCl) with a good current yield (r/ 70%). In contrast,... 

Metallopolymer films have also been prepared by oxidative polymerization of complexes of the type [M(phen)2(4,4 -bipy)2]2+ (M = Fe, Ru, or Os phen= 1,10-phenanthroline, 4,4 -bipy = 4,4 -bipyridine).23 Such films are both oxidatively and reductively electrochromic reversible film-based reduction at potentials below —IV lead to dark purple films,23 the color and potential region being consistent with the viologen dication/radical cation electrochromic response. A purple state at high negative potentials has also been observed for polymeric films prepared from [Ru(L13)3]2+.24 Electropolymerized films prepared from the complexes [Ru(L16)-(bipy)2][PF6]22 and [Ru(L17)3][PF6]226,27 exhibit reversible orange/transparent electrochromic behavior associated with the Run/Ruin interconversion. 

One possible strategy in the development of low-overpotential methods for the electroreduction of C02 is to employ a catalyst in solution in the electrochemical cell, A few systems are known that employ homogeneous catalysts and these are based primarily on transition metal complexes. A particularly efficient catalyst is (Bipy)Re[CO]3Cl, where Bipy is 2,2 bipyridine, which was first reported as such by Hawecker et al. in 1983. In fact, this first report concerned the photochemical reduction of C02 to CO. However, they reasoned correctly that the complex should also be capable of catalysing the electrochemical reduction reaction. In 1984, the same authors reported that (Bipy)Re[C013CI catalysed the reduction of C02 to CO in DMF/water/ tetraalkylammonium chloride or perchlorate with an average current efficiency of >90% at —1.25 V vs. NHE (c. —1.5V vs. SCE). The product analysis was performed by gas chromatography and 13C nmr and showed no other products. 

---