8 Chapter 8Figure 8.1 ORTEP drawing of [IrIII(Cp*)(4,4′‐OMe‐bpy)(OH2)](OTf)2 (3·(OTf)2) w...Scheme 8.1 Catalytic cycle of the reduction of CO2 with H2 using [IrIII(Cp*)(4...Scheme 8.2 Acid–base equilibria of iridium aqua complexes (4–6).Figure 8.2 ORTEP drawing of 2. Hydrogen atoms are omitted for clarity. Selecte...Scheme 8.3 Catalytic cycle of the reduction of CO2 with H2 using [IrIII(Cp*)(4...Figure 8.3 pH Dependence of the formation rate (TOF) of formate in the catalyt...Figure 8.4 pH Dependence of the H2 evolution rate (TOF) in the catalytic hydro...Figure 8.5 Plot of TOF vs. concentration of HCOOH and HCOOK mixture (HCOOH/HCO...Scheme 8.4 Catalytic cycle of the decomposition of HCOOH using [IrIII(Cp*)(4–(...Scheme 8.5 A dinuclear Ir(Cp*) complex with 4,4′,6,6′‐tetrahydroxy‐2,2′‐bipyri...Figure 8.6 Crystal structure of [{Ir(Cp*)(Cl)}2(thbpym)]2+ [370]. C
9 Chapter 9Figure 9.1 ESR spectra of O2·−/M2+ complexes (M2+ = Mg2+, CaFigure 9.2 (a) ESR spectrum observed after irradiation of an 17O (40%) oxygen‐...Scheme 9.1 M n+‐promoted electron transfer from (TPP)Co to O2.Figure 9.3 Plots of log k et vs. ΔE in M n+‐promoted electron transfer from ...Scheme 9.2 M n+‐promoted electron transfer from (TPP)Co to Q.Figure 9.4 Plots of log k et vs. ΔE in electron transfer from (TPP)Co to O2, pr...Figure 9.5 UV–visible absorption spectra of PQ (1.2 × 10−4 M) in the pre...Figure 9.6 (a) UV–visible absorption spectra of PTQ (2.0 × 10−3 M) in th...Figure 9.7 (a) EPR spectrum of PQ·− produced by photoinduced electron tr...Figure 9.8 (a) EPR spectrum of PTQ·− produced by photoinduced electron t...Figure 9.9 CVs of PQ (1.5 × 10−3 M) (a) in the absence of metal ion, and...Figure 9.10 Dependence of the positive shift in E red (ΔE red) of PQ in the pres...Figure 9.11 Plots of E red of PQ (○) and PTQ (Δ) in the presence of M n+ (2....Scheme 9.3 Sc3+‐promoted electron transfer from (TPP)Co to PQ.Figure 9.12 Dependence of k obs on [Sc(OTf)3] for electron transfer from (TPP)C...Scheme 9.4 M n+‐promoted electron transfer from (AcrH)2 to PTQ in MeCN.Figure 9.13 Dependence of k obs on [M n+] for the electron transfer from (Ac...Figure 9.14 (a) Dependence of k obs on [Sc(OTf)3] for electron transfer from Ir...Figure 9.15 EPR spectra of an EtCN solution of Ir(ppy)3 (2.3 × 10−4 M) a...Scheme 9.5 Proportionation equilibrium between QH2 and Q in the presence of ScFigure 9.16 Absorption spectral changes of a deaerated EtCN solution of QH2 (3...Figure 9.17 EPR spectra of a deaerated propionitrile solution of QH2 (3.2 × 10Scheme 9.6 Formation of a chiral assembly [(NQ·−)2–(Sc3+(R)‐pybox)2]Figure 9.18 (a) Positive‐ion ESI mass spectrum of an MeCN solution of NQ (3.0 ...Figure 9.19 Absorbance at 633 nm for cycles of ET reduction of a deaerated MeC...Figure 9.20 The optimized structure of [(Q·−)2–(Sc3+(R)‐pybox)2]+...Scheme 9.7 Sc3+‐promoted electron transfer from (AcrH)2 to TolSQ in MeCN.Figure 9.21 (a) EPR spectrum of TolSQ·−–Sc3+ produced by electron tr...Figure 9.22 Dependence of k et on [Sc3+] for electron transfer from (AcrH)2 Scheme 9.8 Two pathways in electron transfer from electron donors to TolSQ–Sc3...Figure 9.23 Plots of ln(k et T −1) vs. T −1 for electron transfer from...Scheme 9.9 M n+‐promoted intramolecular electron transfer in a ferrocene–na...Figure 9.24 (a) CV of Fc–NQ (5.0 × 10−4 M) in deaerated MeCN containing ...Figure 9.25 Plots of ΔE 1/2 vs. log [M n+] for the one‐electron reduction of...Figure 9.26 (a) EPR spectrum of Fc+–NQ·−/Sc3+ (9.1 mM) produced ...Figure 9.27 Plots of log k ET vs. −ΔG ET in M n+‐promoted intramolecular elec...Scheme 9.10 M n+‐promoted intramolecular electron transfer in a ferrocene–n...Figure 9.28 Plots of −RT ln(k ET[M n+]−1/2) vs. ΔG ET in M n+‐promot...Figure 9.29 (a) ORTEP drawing of Fc–Q. (b) Optimized structure of Ph–Q·− Scheme 9.11 Photoinduced electron transfer from Fc to Q in the Fc–Q dyad, foll...Figure 9.30 CVs of (a) Fc–Q (0.5 mM) and (b) Fc–(Me)Q (0.5 mM) in MeCN contain...Scheme 9.12 M n+‐promoted electron transfer from Fc to Q in Fc–Q and Fc–(Me...Figure 9.31 Plots of log k et vs. ΔE in M n+‐promoted electron transfer in F...Figure 9.32 Formation of a cycloadduct by the reaction of t‐BuBNAH and Q in th...Figure 9.33 Dependence of k obs on [Sc3+] for (a) the cycloaddition reactio...Scheme 9.13 (a) Cycloaddition and (b) hydride transfer pathways via M n+‐pr...Figure 9.34 Crystal structures of (a) [CuIIZnII(bdpi)(MeCN)2](ClO4)3·2MeCN and...Figure 9.35 CVs of (a) [CuZn(bdpi)(MeCN)2]3+ (1.0 mM) and (b) [Cu(MeIm(Py)Scheme 9.14 Formation of the O2·− complex with [ZnII(MeIm(Me)2)]2+.Figure 9.36 EPR spectra of (a) [ZnII(O2·−)(MeIm(Py)2)]+ and (b) [ZnI...Scheme 9.15 The catalytic cycle of the imidazolate‐bridged CuII–ZnII heterodin...Scheme 9.16 Disproportionation of Q·− with [CuZn(bdpi)(MeCN)2]3+.Figure 9.37 Dependence of E red of [(N4Py)FeIV(O)]2+ in MeCN at 298 K on lo...Scheme 9.17 Metal ion‐coupled electron‐transfer reduction of [(N4Py)FeIV(O)]2+...Figure 9.38 Plots of log k 1(circles) and log k 2 (squares) of MCET from ferro...Figure 9.39 (a) ORTEP‐style and (b) chemical structure of the Sc3+‐bound n...Scheme 9.18 Sc3+‐coupled electron‐transfer chain reactions for formation o...Figure 9.40 (a) UV–vis spectral changes showing the conversion from [(Bn‐TPEN)...Figure 9.41 DFT‐optimized structure of [(Bn‐TPEN)MnIV(O)−[Sc(OTf)3]2]2+, c...Figure 9.42 Dependence of E red of [(N4Py)MnIV(O)]2+ (black circles) and [(...Scheme 9.19 Oxidation of a cobalt(III) complex to a cobalt(IV)‐oxo‐metal ion c...Figure 9.43 Dependence of E red of [(N4Py)FeIV(O)]2+ on log [HOTf] (grey ci...Figure 9.44 Plots of k obs vs. [HOTf] (black circles) and [DOTf] (grey circles)...Figure 9.45 UV–vis spectral changes observed in the titration of [(N4Py)MnIV(O...Figure 9.46 Dependence of E red of [(N4Py)MnIV(O)]2+ on the concentration o...Figure 9.47 Plots of log k obs for oxidation of toluene and thioanisole derivat...Figure 9.48 Plots of log k ET for C