Shunichi Fukuzumi - Electron Transfer

7 Chapter 7Scheme 7.1 Photocatalytic reaction of an electron donor (D) and an acceptor (A...Scheme 7.2 Photocatalytic oxygenation of anthracene with O 2using Acr +–Mes...Scheme 7.3 Photocatalytic oxygenation of AnO 2to anthraquinone with Acr + ·...Scheme 7.4 Photocatalytic [2 + 2] cycloaddition of O 2to tetraphenylethylene (...Scheme 7.5 Photocatalytic cis–trans isomerization of stilbene with Acr +–Me...Scheme 7.6 Reaction scheme of photocatalytic oxygenation of p ‐xylene and forma...Scheme 7.7 Photocatalytic mechanism of oxygenation of toluene derivatives (R‐CScheme 7.8 Photocatalytic mechanism of oxygenation of cyclohexane with Acr +...Scheme 7.9 Photocatalytic mechanism of bromination of aromatic compounds with ...Scheme 7.10 Photocatalytic dimerization of 9,10‐dimethylanthracene with Acr +...Figure 7.1 (a) Transient absorption spectra in PhCN observed in photoinduced E...Scheme 7.11 Photocatalytic oligomerization of C 60with Acr +–Mes.Scheme 7.12 Photocatalytic DNA cleavage with Acr +–Mes.Figure 7.2 Agarose gel electrophoresis of photoinduced cleavage of supercoiled...Scheme 7.13 Photocatalytic cycle for intramolecular anti‐Markovnikov hydroethe...Scheme 7.14 Photocatalytic cycle of intermolecular cycloaddition between β‐met...Scheme 7.15 Photocatalytic cycle of anti‐Markovnikov alkene hydroacetoxylation...Scheme 7.16 Photocatalytic cycle of trifluoromethylation of alkenes.Figure 7.3 Time dependence of hydrogen evolution under steady‐state irradiatio...Scheme 7.17 Mechanism of photoinduced reduction of Acr +–Mes with NADH.Scheme 7.18 PCET production of H 2with Acr ·–Mes on PtNPs.Scheme 7.19 Structure of QuPh +–NA and the overall catalytic cycle for the ...Figure 7.4 Photocatalytic production of H 2from oxalate with QuPh +–N incor...Scheme 7.20 The catalytic cycle for the photocatalytic hydrogen evolution with...

8 Chapter 8Figure 8.1 ORTEP drawing of [Ir III(Cp *)(4,4′‐OMe‐bpy)(OH 2)](OTf) 2( 3·(OTf) 2) w...Scheme 8.1 Catalytic cycle of the reduction of CO 2with H 2using [Ir III(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 CO 2with H 2using [Ir III(Cp *)(4...Figure 8.3 pH Dependence of the formation rate (TOF) of formate in the catalyt...Figure 8.4 pH Dependence of the H 2evolution 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 [Ir III(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 H bond...Scheme 8.6 Catalytic mechanism for interconversion between NADH and H 2with wa...Figure 8.7 Plot of TOF for catalytic hydrogen evolution vs. the concentration ...Figure 8.8 pH Dependence of the rate (TOF) of H 2evolution in the oxidation of...Figure 8.9 Plot of TOF vs. the concentration of NAD +in the catalytic hydr...Scheme 8.7 Formation of a hydride complex 7in the hydrogenation of 6 with ali...Figure 8.10 Change in absorbance at λ = 350 nm due to formation of the hy...Scheme 8.8 Catalytic cycle of hydrogen evolution from ethanol using [Ir III(Cp *Scheme 8.9 Photoconversion from a hydride complex 7to 9.Figure 8.11 Time course of hydrogen evolution from 2‐propanol (4.3 M) catalyze...Scheme 8.10 Catalytic cycles for decomposition of paraformaldehyde to H 2and f...

9 Chapter 9Figure 9.1 ESR spectra of O 2· −/M 2+complexes (M 2+= Mg 2+, 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 O 2.Figure 9.3 Plots of log k etvs. Δ E 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 etvs. Δ E in electron transfer from (TPP)Co to O 2, pr...Figure 9.5 UV–visible absorption spectra of PQ (1.2 × 10 −4M) in the pre...Figure 9.6 (a) UV–visible absorption spectra of PTQ (2.0 × 10 −3M) 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 −3M) (a) in the absence of metal ion, and...Figure 9.10 Dependence of the positive shift in E red(Δ E red) of PQ in the pres...Figure 9.11 Plots of E redof PQ (○) and PTQ (Δ) in the presence of M n+(2....Scheme 9.3 Sc 3+‐promoted electron transfer from (TPP)Co to PQ.Figure 9.12 Dependence of k obson [Sc(OTf) 3] for electron transfer from (TPP)C...Scheme 9.4 M n+‐promoted electron transfer from (AcrH) 2to PTQ in MeCN.Figure 9.13 Dependence of k obson [M n+] for the electron transfer from (Ac...Figure 9.14 (a) Dependence of k obson [Sc(OTf) 3] for electron transfer from Ir...Figure 9.15 EPR spectra of an EtCN solution of Ir(ppy) 3(2.3 × 10 −4M) a...Scheme 9.5 Proportionation equilibrium between QH 2and Q in the presence of ScFigure 9.16 Absorption spectral changes of a deaerated EtCN solution of QH 2(3...Figure 9.17 EPR spectra of a deaerated propionitrile solution of QH 2(3.2 × 10Scheme 9.6 Formation of a chiral assembly [(NQ· −) 2–(Sc 3+( 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–(Sc 3+(R)‐pybox) 2] +...Scheme 9.7 Sc 3+‐promoted electron transfer from (AcrH) 2to TolSQ in MeCN.Figure 9.21 (a) EPR spectrum of TolSQ· −–Sc 3+produced by electron tr...Figure 9.22 Dependence of k eton [Sc 3+] for electron transfer from (AcrH) 2Scheme 9.8 Two pathways in electron transfer from electron donors to TolSQ–Sc 3...Figure 9.23 Plots of ln( k et T −1) vs. T −1for 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 −4M) in deaerated MeCN containing ...Figure 9.25 Plots of Δ E 1/2vs. log [M n+] for the one‐electron reduction of...Figure 9.26 (a) EPR spectrum of Fc +–NQ· −/Sc 3+(9.1 mM) produced ...Figure 9.27 Plots of log k ETvs. −Δ G ETin 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. Δ G ETin 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 etvs. Δ E 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 obson [Sc 3+] 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) [Cu IIZn II(bdpi)(MeCN) 2](ClO 4) 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 O 2· −complex with [Zn II(MeIm(Me) 2)] 2+.Figure 9.36 EPR spectra of (a) [Zn II(O 2· −)(MeIm(Py) 2)] +and (b) [Zn I...Scheme 9.15 The catalytic cycle of the imidazolate‐bridged Cu II–Zn IIheterodin...Scheme 9.16 Disproportionation of Q· −with [CuZn(bdpi)(MeCN) 2] 3+.Figure 9.37 Dependence of E redof [(N4Py)Fe IV(O)] 2+in MeCN at 298 K on lo...Scheme 9.17 Metal ion‐coupled electron‐transfer reduction of [(N4Py)Fe IV(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 Sc 3+‐bound n...Scheme 9.18 Sc 3+‐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)Mn IV(O)−[Sc(OTf) 3] 2] 2+, c...Figure 9.42 Dependence of E redof [(N4Py)Mn IV(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 redof [(N4Py)Fe IV(O)] 2+on log [HOTf] (grey ci...Figure 9.44 Plots of k obsvs. [HOTf] (black circles) and [DOTf] (grey circles)...Figure 9.45 UV–vis spectral changes observed in the titration of [(N4Py)Mn IV(O...Figure 9.46 Dependence of E redof [(N4Py)Mn IV(O)] 2+on the concentration o...Figure 9.47 Plots of log k obsfor oxidation of toluene and thioanisole derivat...Figure 9.48 Plots of log k ETfor C H bond cleavage of toluene derivatives and ...Scheme 9.20 Unified mechanism of oxidation of toluene and thioanisol derivativ...Figure 9.49 Electron‐transfer driving force (−Δ G et) dependence of log k oxfor ...Figure 9.50 UV–vis spectra of [(TMC)Fe III(O 2)]–M n+complexes (M n+= ScFigure 9.51 Plot of hν maxof [(TMC)Fe III(O 2)] +–M n+complexes vs. ...