Coupling Reactions Using Excited State Organonickel Complex _LS_Daiki_Kamakura

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1 Coupling eactions Using Excited State rganonickel Complex _LS_Daiki_Kamakura

2 i Catalysis in Coupling eactions Co 28 i Cu h Pd Ag Ir Pt Au Features of i d electrons: 8 relatively inexpensive (i: $1/g, Pd: $183/g, Pt: $483/g) easier accessibility of i 0 /i I /i II /ii II /i IV oxidation states Coupling reactions using i catalysis coupling with nucleophile i X + M coupling with electrophile i X + X C-H activation i H + X = sp 3, sp 2 X =. Br, I, Tf, Me, H H H = sp 3, sp 2, sp, 2,, H M = B 2, MgX, ZnX, SiX 3 In all of these reactions, ground state i complex was used. So excited-state metal catalysts remains largely unexploited. etherton, M.., Fu, G. C. Adv. Synth. Catal. 2004, 346,1525. Tasker, S. Z., Standley, E. A., Jamison, T. F. ature, 2014, 509, 299. Su, B., Cao, Z-C., Shi, Z-J. Acc, Chem es, 2015, 48, 886. Ananikov, V. P. ACS Catal. 2015, 5,

3 Photo eactions of Metal Complex assical reactions ligand elimination Cr(C) 6 h Cr(C) 5 + C ligand exchange Cp* H Ir Ph 3 P H h C 6 H 12 Cp* H Ir Ph 3 P C 6 H 11 Janowicz, A. H., Bergman,. G. J. Am. Chem. Soc, 1983, 105, ecently reported chlorine photoelimination Ph 2 P P Ph 2 i III h Ph 2 P P Ph 2 * i III Ph 2 P P Ph 2 i II Hwang, S. J., Powers, D. C. Maher, A. G., Anderson, B. L., Hadt,. G., Zheng, S-L., Chen, Y-S., ocera, D. G. J. Am. Chem. Soc, 2015, 137,

4 Contents 1. Direct C(sp 3 ) H Cross Coupling Enabled by Catalytic Generation of Chlorine adicals (Doyle, 2016) 2. Photosensitized, Energy Transfer Mediated rganometallic Catalysis through Electronically Excited ickel(ii) (MacMillan, 2017) 3

5 Contents 1. Direct C(sp 3 ) H Cross Coupling Enabled by Catalytic Generation of Chlorine adicals (Doyle, 2016) 2. Photosensitized, Energy Transfer Mediated rganometallic Catalysis through Electronically Excited ickel(ii) (MacMillan, 2017) 4

6 C-H Functionalization of Amines with yl Halides Ir III (2 mol%) I i II 2 glyme (10 mol%) + dtbbpy (15 mol%) Ph H Ph KH (3 eq.), DMF (0.04 M) 34W Blue LED, rt (3 equiv.) Proposed mechanism Ph Ir III*, h H + Ir II Ph Ph Ph I, i 0 Ii III Ph i I I Ph Ir II i 0 + Ir III F 3 C F 3 C Ir III F F F F + PF6 Ahneman, D. T., Doyle, A. G. Chem. Sci, 2016, 7, Ir III = [Ir III (df-cf 3 -ppy) 2 (dtbpy)]pf 6 5

7 Difficulty of Application for α-ylation of Ether Ir III* H + i 0 H H Ir II I not reported E 1 / 2 (Ir III* /Ir II ) = 1.21 V Usage of more storong oxidant C E 1 / 2 (THF + /THF) = 1.75 V E 1 / 2 (Ph 2 + /Ph 2 ) = 0.70 V = (CH 2)4 E 1 / 2 (DCA * /DCA ) = 2.07 V xidation of THF: disfavored (ΔE = 0.69 V) xidation of Amine: favored (ΔE = 0.51 V) xidation of THF: favored (ΔE= 0.32 V) C DCA E 1 / 2 (i I /i 0 ) = 1.2 V E 1 / 2 (DCA/DCA ) = 1.01 V E 1 / 2 (Ir III /Ir II ) = 1.37 V eduction of i I by DCA : disfavored (ΔE= 0.2 V) eduction of i I by Ir II : favored (ΔE= 0.36 V) Ir III = [Ir III (df-cf 3 -ppy) 2 (dtbpy)]pf 6, i I = (dtbpy)i I Br A + B + + e A + e B E 1 / 2 (A + /A) = xx V E 1 / 2 (B + /B) = yy V ΔG = FΔE F: Faraday constant ΔE>0 ΔG<0 A + + B A + B + ΔE = (xx yy) V ΔE = 0.1 V ~ ΔG = 2.3kcal/mol 6

8 Doyle s Working Hypothesis for α-ylation of Ether Ph 2 P P Ph 2 i III h Doyle s Working Hypothesis Ph 2 P P Ph 2 * i III P Ph 2 Hwang, S. J., Powers, D. C. Maher, A. G., Anderson, B. L., Hadt,. G., Zheng, S-L., Chen, Y-S., ocera, D. G. J. Am. Chem. Soc, 2015, 137, 6472 Ph 2 P i II + H Ir III, i 0 h i II Ir III* ; h [i III ] + * [i II ] + Ir II THF BDE THF: 92 kcal/mol H-: 102 kcalmol H Shieds, B. J., Doyle, A. G. J. Am. Chem. Soc. 2016, 138,

9 ptimization of THF α-ylation eaction Ac entry 1 + H (X equiv.) photocatalyst [Ir III (df-cf 3 -ppy) 2 (dtbpy)]pf 6 Photocatalyst (2 mol%) i(cod) 2 (10 mol%) dtbbpy (15 mol%) K 3 P 4 (2 eq.), solvent (0.04 M) 34W Blue LED, rt, 72 h THF (X equiv.) solvent Ac yield 1 benzene 20 2 [Ir III (df-cf 3 -ppy) 2 (dtbpy)]pf 6 10 benzene 71 F 3 C F 3 C F Ir III F + PF6 F F [Ir III (df-cf 3 -ppy) 2 (dtbpy)]pf [Ir III (df-cf 3 -ppy) 2 (dtbpy)]pf 6 THF (0.04 M) 92 none THF (0.04 M) 0 5 a [Ir III (df-cf 3 -ppy) 2 (dtbpy)]pf 6 THF (0.04 M) 0 6 b [Ir III (df-cf 3 -ppy) 2 (dtbpy)]pf 6 THF (0.04 M) 0 a i(cod) 2 was not added. b eaction was conducted in the dark. Shieds, B. J., Doyle, A. G. J. Am. Chem. Soc. 2016, 138,

10 Sutoichiometric xidation Experiment i II [TBPA]Sb 6 (1 eq.) K 3 P 4 (2 eq.), THF (2 mm) 34W Blue LED 78 ºC, 72 h i III h + + entry 1 conditions see above 6% - 32% THF 20% 2 no oxidant 3% 62% 0% 3 dark 63% 9% 0% Br SbF 6 3 [TBPA]Sb 6 E 1 / 2 ( 3 + / 3 ) = 1.16 V E 1 / 2 (i III /i II ) = 0.85 V i II = (tbbpy)i II (tol) Shieds, B. J., Doyle, A. G. J. Am. Chem. Soc. 2016, 138,

11 eactivity of yl Halides Me X + H (0.04 M) [Ir III (df-cf 3 -ppy) 2 (dtbpy)]pf 6 (2 mol%) i(cod) 2 (10 mol%) dtbbpy (15 mol%) K 3 P 4 (2 eq.) additive 34W Blue LED, rt, 72 h Me entry X additive yield 1 none 68% 2 Br none 10% 3 I none 5% BDE THF: 92 kcal/mol H : 102 kcalmol H Br: 87 kcal/mol H I: 71 kcal/mol H X 4 I TBAC 51% i II I l i II 5 I TBAI 6% TBA: tetrabutylammonium Shieds, B. J., Doyle, A. G. J. Am. Chem. Soc. 2016, 138,

12 Proposed Catalytic Cycle Lni 0 SET Ir II L i II n Lni I Ir III h Ir III* SET L i III n L n i III L i III n + L n i II h * L i III n H Shieds, B. J., Doyle, A. G. J. Am. Chem. Soc. 2016, 138, H Ir III = [Ir III (df-cf 3 -ppy) 2 (dtbpy)]pf 6 11

13 Substrate Scope of yl Chloride + H (0.04 M) [Ir III (df-cf 3 -ppy) 2 (dtbpy)]pf 6 (2 mol%) i(cod) 2 (10 mol%) dtbbpy (15 mol%) K 3 P 4 (2 eq.) 34W Blue LED, rt, 36~72 h = Me: 70% = Ph: 86% = Ph: 77% = C: 83% = Ac: 79% = Bz: 76% Me 51% Me Boc 69% F 3 C 78% 93% Shieds, B. J., Doyle, A. G. J. Am. Chem. Soc. 2016, 138,

14 Substrate Scope of Ether and Hydrocarbon Ac + H (0.04 M) [Ir III (df-cf 3 -ppy) 2 (dtbpy)]pf 6 (2 mol%) i(cod) 2 (10 mol%) dtbbpy (15 mol%) K 3 P 4 (2 eq.) 34W Blue LED, rt, 36~72 h Ac ether X Me Me Ph Ac Ac Ac X = CH 2 : 58% X = : 78% 91% (branch: linear = 1.35 : 1) 47% hydrocarbon Ac 71% Shieds, B. J., Doyle, A. G. J. Am. Chem. Soc. 2016, 138, Ac 41% a a 10 eq. of cyclohexane was used. eaction was conducted in benzene (0.04 M). 13

15 Computational Studies A B i III transitions with > 10% i, σ σ* contributions: A: 375, B: 401 nm reaction was conducted under blue LED (λ>400 nm) so transition B would raise i dissociation Fig. 1. Calculated absorption spectrum (solid black line) and oscillators (solid bars; red bars: transitions with > 10% i, σ σ* contributions) from TD- DFT calculations on [iiii(dtbbpy)(ph)] +. calc. BDE of [(dtbpy)(tol)i III ] + : 56 kcal/mol Fig. 2. Transition orbitals for excited state B of [i(dtbbpy)(ph)]+ ( This transition has a large i σ σ* component). i could be cleaved by transition B (401 nm > 71 kcal/mol ) Shieds, B. J., Doyle, A. G. J. Am. Chem. Soc. 2016, 138, For all calculations the B3LYP hybrid exchange-correlation functional was used. Gas-phase geometry optimization 14 and frequency calculations were carried out using a SDD basis set for i and and 6-31G* for all other atoms.

16 Short Summary + H Ir III = (2 mol%) i(cod) 2 (10 mol%) dtbbpy (15 mol%) K 3 P 4 (2 eq.) 34W Blue LED, rt i III * H + i II Ir III = [Ir III (df-cf 3 -ppy) 2 (dtbpy)]pf 6 Shieds, B. J., Doyle, A. G. J. Am. Chem. Soc. 2016, 138,

17 Contents 1. Direct C(sp 3 ) H Cross Coupling Enabled by Catalytic Generation of Chlorine adicals (Doyle, 2016) 2. Photosensitized, Energy Transfer Mediated rganometallic Catalysis through Electronically Excited ickel(ii) (MacMillan, 2017) 16

18 Coupling of yl Halide with xygen ucleophiles Br + H i II Photocatalyst (1 mol%) i 2 glyme (5 mol%) dtbbpy (5 mol%) quinuclidine (10 mol%) K 2 C 3 (1 eq.), CH 3 C Blue LED, rt, 24 h Ir III* Ir II i III F 3 C F 3 C F Ir III F + PF6 F F [Ir III (df-cf 3 -ppy) 2 (dtbpy)]pf 6 Terrett, J. A., Cuthbertson, J. D., Shurtleft, V. W., MacMillan, D. W. C. ature, 2015, 524, 330. Br + C 2 H Photocatalyst (1 mol%) i 2 glyme (10 mol%) dtbbpy (15 mol%) Cs 2 C 3 (1.5 eq.), DMF Blue LED, rt, 72 h C 2 Ir III, hv i II Ir IV + C 2 Br C 2 not obtained Zuo, Z., Ahneman, D. T., Chu, L., Terrett, J. A., Doyle, A. G. Macmillan, D. W. C. Science, 2014, 6195,

19 Difficulty of Coupling eaction with carboxylic Acid Ir III, hν i0 IrII C 2 X i 0, X C i II Ir III, hν Ir II C i III i I C not reported E 1 / 2 (Ir III* /Ir II ) = 1.21 V E 1 / 2 (C 2 /C 2 Cs) = 0.95 V E 1 / 2 (i III /i II ) = 1.00 V xidation of C 2 Cs: favored (ΔE = 0.26 V) xidation of i II : favored (ΔE = 0.21 V) Ir III = [Ir III (df-cf 3 -ppy) 2 (dtbpy)]pf 6 C 2 Cs = Boc Pro Cs i II is exists only catalytic ammount so selective oxidation of i II complex would be difficult To surpless oxidation of carboxilic acid, usage of weaker oxidant is necessary, but it makes difficult to oxidize i II to i III. Welin, E.., Le. C., ias,. D. M., McCusker, J. K., MacMillan, D. W. C. Science, 2017, 355, 380, 18

20 Coupling of yl Bromide with Carboxylic Acid Me 2 C Br + PhC 2 H (2 equiv.) Photocatalyst (1 mol%) i(cod) 2 (10 mol%) dtbbpy (10 mol%) Hi-Pr (2 equiv.) DMF(0.2 M) 26W CFL, 40 ºC, 24 h Me 2 C Ph entry ligand E 1 / 2 (Ir III* /Ir II ) (V) yield 4,4 -(CF 3 ) 2 -bpy ,4 -(C 2 Me) 2 -bpy bpy ,4 -Me 2 -bpy ,4 -(Me) 2 -bpy ppy strong oxidant oxidizing power weak oxidant 4 5 X Ir III + PF6 Photocatalyst = [Ir III (ppy) 2 (ligand)]pf 6 Ir III = [Ir III (df-cf 3 -ppy) 2 (dtbpy)]pf 6 E 1 / 2 (Ir III* /Ir II ) = 1.21 V E 1 / 2 (i III /i II ) = 1.00 V Welin, E.., Le. C., ias,. D. M., McCusker, J. K., MacMillan, D. W. C. Science, 2017, 355, 380, 19

21 Energy of the Ir-Based Exited State Me 2 C Br + PhC 2 H (2 equiv.) Photocatalyst (1 mol%) i(cod) 2 (10 mol%) dtbbpy (10 mol%) Hi-Pr (2 equiv.) DMF(0.2 M) 26W CFL, 40 ºC, 24 h Me 2 C Ph entry 1 ligand E 1 / 2 (Ir III* /Ir II ) (V) E T (kcal/mol)* yield 4,4 -(CF 3 ) 2 -bpy strong oxidant low energy potential 2 4,4 -(C 2 Me) 2 -bpy bpy 4,4 -Me 2 -bpy 4,4 -(Me) 2 -bpy oxidizing power triplet state energy 6 ppy Photocatalyst = [Ir III (ppy) 2 (ligand)]pf 6 * E T was caluculated from MAX of emission spectrum. weak oxidant high energy potential Welin, E.., Le. C., ias,. D. M., McCusker, J. K., MacMillan, D. W. C. Science, 2017, 355, 380, 20

22 Direct Excitation Experiment Me 2 C Br + PhC 2 H (2 equiv.) Photocatalyst (1 mol%) i(cod) 2 (10 mol%) dtbbpy (10 mol%) Hi-Pr (2 equiv.) DMF(0.04 M) 40 W Blue LED, 40 ºC, time Me 2 C Ph entry Photocatalyst time (h) yield 0 1 Ir(ppy) 3 Ph Ph % 25% (brsm: 63%) Ir III 2 none % (brsm: 100%) [Ir III (ppy) 3 ] 3 a none 120 0% a eaction vessel was wrapped in aluminium foil and placed in front of blue LED. coupring reaction would undergo via energy transfer pathway Welin, E.., Le. C., ias,. D. M., McCusker, J. K., MacMillan, D. W. C. Science, 2017, 355, 380, 21

23 Stoichiometric Studies with ylnickel(ii) Complex Me Me i II F 3 C Me CF3 Photocatalyst (0.625 mol%) Hi-Pr (2 equiv.) DMF-d 7 (0.01 M) 40 W Blue LED, 40 ºC, time CF 3 CF 3 Me entry 1 Photocatalyst Ir(ppy) 3 time (h) 30 min CMe a detected Ir III 2 none 60 h detected 3 b none 60 h not detected [Ir III (ppy) 3 ] a eaction was accessed by 19 F M. b eaction vessel was wrapped in aluminium foil and placed in front of blue LED. Welin, E.., Le. C., ias,. D. M., McCusker, J. K., MacMillan, D. W. C. Science, 2017, 355, 380, 22

24 Proposed Catalytic Cycle Br Lni 0 C * L i II n Br L i II n Ir III* ET L i II n C Br C 2 hν Ir III Welin, E.., Le. C., ias,. D. M., McCusker, J. K., MacMillan, D. W. C. Science, 2017, 355, 380, 23

25 Substrate Scope of Carboxylic Acid Me 2 C Br + C 2 H (2 equiv.) [Ir III (ppy) 3 ] (1 mol%) i(cod) 2 (5 mol%) dtbbpy (5 mol%) Hi-Pr (2 equiv.) DMF(0.2 M) 26W CFL, 40 ºC, 18 h Me 2 C Me Me 2 C Me 2 C Me 2 C = Me:76% = c-hex: 81% = : 79% = Ad: 80% 83% X 76% H Cbz Me 2 C Me 2 C Me 2 C 80% X = F: 93% X = Me: 95% = Ph: 86% = i-pr: 81% Welin, E.., Le. C., ias,. D. M., McCusker, J. K., MacMillan, D. W. C. Science, 2017, 355, 380, 24

26 Substrate Scope of yl Bromide Br + PhC 2 H (2 equiv.) [Ir III (ppy) 3 ] (1 mol%) i(cod) 2 (5 mol%) dtbbpy (5 mol%) Hi-Pr (2 equiv.) DMF(0.2 M) 26W CFL, 40 ºC, 18 h Ph Ph Ph Ph C = Ac: 86% = CF 3 : 86% F = 81% = : 68% = CF 3 : 86% Ph F 3 C Ph Ph = Me: 95% = CF 3 : 87% 62% = Me: 84% = CF 3 : 86% Welin, E.., Le. C., ias,. D. M., McCusker, J. K., MacMillan, D. W. C. Science, 2017, 355, 380, 25

27 Possible Energy Transfer Mechanism 1 Förster resonance energy transfer nonradiative dipole dipole coupling efficiency is depends on the overlap integral of the donor emission spectrum with the acceptor absorption distance between D and A: 10~100 Å 2 Dexter energy transfer electron exchange between A and D efficiency is depends on the wavefunction overlap between the donor and acceptor Donor Acceptor D A D A D A distance between D and A: <10Å i II : Ir III = 5 : 1 Me Me Me i II F 3 C CF3 Ir III i II Dexter transfer is likely Figure 3. Electronic Absorption Spectrum. Main graph: Electronic playing an important role in absorption spectrum of i II. Inset: verlap between the emission of the reductive elimination step Ir III * and the absorbance of i II. Welin, E.., Le. C., ias,. D. M., McCusker, J. K., MacMillan, D. W. C. Science, 2017, 355, 380, 26 i II Ir III small degree of overlap

28 Detailed Excitation Mechanism i II : Ir III = 5 : 1 i II + Ir III (calculated) i II + Ir III (observed) Me Me i II F 3 C Me CF3 association between i II and Ir III was suggested Ir III œä œä interaction between dmbpy and ppy? S 1 (Ir III ) Figure 4. UV-Vis spectrum of i II and Ir III S 1 (i II ) S 1 (Ir III ) S 1 (i II ) hν T 1 (Ir III ) T 1 (i II ) energy transfer T 1 (Ir III ) T 1 (i II ) (Dexter mechanism) S 0 (Ir III ) S 0 (i II ) Ir III i II Ir III i II ground state association S 0 (Ir III ) S 0 (i II ) Ir III [i II ]* Welin, E.., Le. C., ias,. D. M., McCusker, J. K., MacMillan, D. W. C. Science, 2017, 355, 380, 27

29 Proposed Mechanism for. E. (My proposal) π* of ppy (MLCT) S 1 (Ir III ) π* of ppy (MLCT) S 1 (i II ) π* of dmbpy? (MLCT) hν T 1 (Ir III ) [Ir IV (ppy )(ppy) 2 ]* T 1 (i II ) S 0 (Ir III ) [Ir III (ppy) 3 ] hν [Ir III (ppy) 3 ]* S 0 (i II ) [(dmbpy)i II ()(CMe)] It is well known that transition S 0 (Ir III ) to S 1 (Ir III ) and T 1 (Ir III ) is metal to ligand charge transfer (MLCT) If transition S 0 (i II ) to T 1 (i II ) is MLCT (i II to dmbpy), electron deficient i III+ would undergo reductive relimination [(dmbpy)i II ()(CMe)]* [(dmbpy )i III ()(CMe)]* [(dmbpy )i I ]* dmbpy = 4,4-dimethoxybipyridine CMe Welin, E.., Le. C., ias,. D. M., McCusker, J. K., MacMillan, D. W. C. Science, 2017, 355, 380, 28

30 Summary + H Ir III (2 mol%) i(cod) 2 (10 mol%) dtbbpy (15 mol%) K 3 P 4 (2 eq.) 34W Blue LED, rt i III * H + i II Ir III = [Ir III (df-cf 3 -ppy) 2 (dtbpy)]pf 6 Shieds, B. J., Doyle, A. G. J. Am. Chem. Soc. 2016, 138, Br + C 2 H Ir(ppy) 3 (1 mol%) i(cod) 2 (5 mol%) dtbbpy (5 mol%) Hi-Pr (2 equiv.) DMF(0.04 M) 26W CFL, 40 ºC i II * Welin, E.., Le. C., ias,. D. M., McCusker, J. K., MacMillan, D. W. C. Science, 2017, 355, 380, 29

31 Appendix 30

32 Absorbance of [i III 3 ] + Complex Black: [Li III 3 ] + ed: Li II 2 Ph 2 P P Ph 2 i III hν Ph 2 P P Ph 2 * i III Ph 2 P P Ph 2 i II Hwang, S. J., Powers, D. C. Maher, A. G., Anderson, B. L., Hadt,. G., Zheng, S-L., Chen, Y-S., ocera, D. G. J. Am. Chem. Soc, 2015, 137,

33 Halogene Exchange Experiment Me I + H (0.04 M) [Ir III (df-cf 3 -ppy) 2 (dtbpy)]pf 6 (2 mol%) i(cod) 2 (10 mol%) dtbbpy (15 mol%) K 3 P 4 (2 eq.) TBA (1 equiv.) 34W Blue LED, rt, 72 h Me Shieds, B. J., Doyle, A. G. J. Am. Chem. Soc. 2016, 138,

34 Lamp Emission Data (Doyle s Work) Shieds, B. J., Doyle, A. G. J. Am. Chem. Soc. 2016, 138,

35 Absorbance of [(tbbpy)i II (tol)] i II Shieds, B. J., Doyle, A. G. J. Am. Chem. Soc. 2016, 138,

36 Stoichiometric xidation Using Ir III as an xidant i II [Ir III (df-cf 3 -ppy) 2 (dtbpy)]pf 6 (20 mol%) THF (12.5 mm) 34W Blue LED, rt, 3 h + 7% 33% Shieds, B. J., Doyle, A. G. J. Am. Chem. Soc. 2016, 138,

37 Cyclic Voltammetry Data i II Shieds, B. J., Doyle, A. G. J. Am. Chem. Soc. 2016, 138,

38 Calculated elevant Molecular rbitals Calculations were performed on Gaussian 09 D.01 software suite (37). For all calculations the B3LYP hybrid exchange-correlation functional was used. Gasphase geometry optimization and frequency calculations were carried out using a SDD basis set for i and and 6-31G* for all other atoms. ptimization and frequency calculations for thermochemistry were carried out using a SDD basis for i and and G** for all other atoms with the SMD (THF) solvation model. All frequency calculations gave no imaginary frequencies. Time-dependent DFT (TD-DFT) calculations were carried out on the gas-phase optimized geometry using the TZVP basis set. Shieds, B. J., Doyle, A. G. J. Am. Chem. Soc. 2016, 138,

39 DFT-Calculated Transitions Shieds, B. J., Doyle, A. G. J. Am. Chem. Soc. 2016, 138,

40 ptimization of eaction Conditions Welin, E.., Le. C., ias,. D. M., McCusker, J. K., MacMillan, D. W. C. Science, 2017, 355, 380, 39

41 Emission Spectrum of Ir III Complexes Welin, E.., Le. C., ias,. D. M., McCusker, J. K., MacMillan, D. W. C. Science, 2017, 355, 380, 40

42 Cyclic Voltammetry Data Me Me Me i II F 3 C CF 3 Welin, E.., Le. C., ias,. D. M., McCusker, J. K., MacMillan, D. W. C. Science, 2017, 355, 380, 41

43 Quenching Experiments Ir III absorbance at 400 nm was used Me Me Me i II F 3 C CF3 (quencher) I 0 /I = 1 + k q t 0 [Q] Welin, E.., Le. C., ias,. D. M., McCusker, J. K., MacMillan, D. W. C. Science, 2017, 355, 380, 42

44 Quenching Experiments Ir III Me Me Me i II F 3 C CF3 (quencher) Figure S19. Time-esolved Stern-Volmer Experiment. Welin, E.., Le. C., ias,. D. M., McCusker, J. K., MacMillan, D. W. C. Science, 2017, 355, 380, 43

45 Excitation of Ir III (ppy) 3 MacMillan, D. W. C. ature ev. 2017, 52,1, 44

46 xidative and eductive Quenching Cycle of [u(bpy) 3 ] 2+ MacMillan, D. W. C. Chem. ev. 2013, 113,

Metallaphotoredox Catalysis (Including my work in Shū Kobayashi group from Oct to Aug. 2015)

Metallaphotoredox Catalysis (Including my work in Shū Kobayashi group from Oct to Aug. 2015) tallaphotoredox (ncluding my work in Shū Kobayashi group from ct. 2013 to Aug. 2015) otoredox Transition tal Tatsuhiro Tsukamoto Literature Talk: Jan. 6 th, 2016 the Dong group 1 Contents 1. Visible Light