Dinuclear Nickel Complexes in Five States of Oxidation Using a Redox-Active Ligand. Supporting Information

Transcription

1 Dinuclear ickel omplexes in Five States of Oxidation Using a Redox-Active Ligand You-Yun Zhou, Douglas R. artline, Talia J. Steiman, Phillip E. Fanwick, and hristopher Uyeda Supporting Information 1. 1 MR, 13 MR, and EPR Spectra S2 2. UV-Vis Spectra S10 3. IR Spectra S13 4. yclic Voltammograms S16 5. XRD Data S17 6. omputational Methods and Optimized Structures S24 S1

2 1. 1 MR, 13 MR, and EPR Spectra Figure S1. 1 MR spectrum for ( i-pr DI) 1 in Dl 3 (room temperature). Figure S2. 13 { 1 } MR spectrum for ( i-pr DI) 1 in Dl 3 (room temperature). S2

3 Figure S3. 1 MR spectra for the reaction between i(od) 2 (2.0 equiv) and i-pr DI (1.0 equiv) in 6 D 6 (spectra and reaction at room temperature). Figure S4. 1 MR spectrum for ( i-pr DI)i 2 ( 6 6 ) 2 in 6 D 6 (room temperature). S3

4 f1 (ppm) Figure S5. 13 { 1 } MR spectrum for ( i-pr DI)i 2 ( 6 6 ) 2 in 6 D 6 (room temperature). Me i-pr i i i-pr (TF) 3 K i-pr Me i-pr Figure S6. Room temperature solution (298 K, TF) ) X-band EPR spectrum for (TF) 3 K[( i- Pr DI)i 2 ( 6 6 )] 3. Simulated parameters: g iso = S4

5 Figure S7. Frozen solution (125 K, TF) X-band EPR spectrum for (TF) 3 K[( i-pr DI)i 2 ( 6 6 )] 3. Simulated parameters: g 1 = 2.037, g 2 = 2.097, g3 = g m max g min = Figure S8. Frozen solution (125 K, TF) X-band EPR spectrum for (TF) 3 K[( i-prdi )i 2 ( 6 6 )] 3 highlightingg the nitrogen hyperfinee coupling. A hyperfine coupling constant for nitrogen of 15 Mz was estimated. S5

6 Figure S9. 1 MR spectrum for ( i-pr DI)i 2 Br 2 4 in 6 D 6 (room temperature). Figure S10. Variable temperature ( 60 to 50 o ) 1 MR spectrum for ( i-pr DI)i 2 Br 2 4 in TF. S6

7 Figure S11. urie plots of the paramagnetically-shifted 1 MR signals for ( i-pr DI)i 2 Br 2 4 in TF ( 60 to 50 o ). i-pr Me Me i-pr i i Br i-pr i-pr Figure S12. Solution EPR spectrum (298 K, 2-MeTF) for ( i-pr DI)i 2 Br 5. Simulated parameters: g iso = S7

8 Figure S13. Frozen solution EPR spectrum (125 K, 2-MeTF) for ( i-pr DI)i 2 Br 5. Simulated parameters: g 1 = 2.050, g 2 = 2.037, g 3 = g max g min = f1 (ppm) Figure S14. 1 MR spectrum for [( i-pr DI)i 2 Br 2 (Me) 2 ]PF 6 6 in D 3 (room temperature). S8

9 Figure S15. Variable temperature ( 34 to 70 o ) 1 MR spectrum for [( i-pr DI)i 2 Br 2 (Me) 2 ]PF 6 6 in D 3. Figure S16. urie plots of the paramagnetically-shifted Pr DI)i 2 Br 2 (Me) 2 ]PF 6 6 in D3 ( 34 to 70 o ). 1 MR signals for [( i- S9

10 2. UV-Vis Spectra ε / cm -1 M λ / nm Figure S17. Room temperature UV-Vis spectrum for ( i-pr DI)i 2 ( 6 6 6) 2 in TF (0.064 mm) ). Figure S18. Room temperature IR spectrum for ( i-pr DI)i 2 ( 6 6 ) 2 in TF (0.075 mm). S10

11 ε / cm -1 M λ / nm Figure S19. Room temperature UV-Vis spectrum for ( i-pr DI)i 2 Br 2 4 in TF (0.056 mm). ε / cm -1 M λ / nm Figure S20. Room temperature UV-visible spectrum for ( i-pr DI)i 2 Br 5 in TF (0.059 mm). S11

12 ε / cm -1 M λ / nm Figure S21. Room temperature UV-visible spectrum for [( i-pr DI)i 2 (Me) 2 Br 2 ]PF 6 6 in TF (0.105 mm). S12

13 3. IR Spectra Figure S22. ATR-IR spectrum for ( i-pr DI) 1. Figure S23. ATR-IR spectrum for ( i-pr DI)i 2 ( 6 6 ) 2. S13

14 Figure S24. ATR-IR spectrum for ( i-pr DI)i 2 Br 2 4. Figure S25. ATR-IR spectrum for ( i-pr DI)i 2 Br 5. S14

15 Figure S26. ATR-IR spectrum for [( i-pr DI)i2(Me) 2 2 Brr 2 ]PF 6 6. Figure S27.. A comparison of the ATR-IR spectrum for (a) ( i-pr DI) 1, (b) [( i- Pr DI)i 2 (Me) 2 Br 2 ]PF 6 6, (c) ( i-pr DI)i 2 Br 2 4, (d) ( i-pr DI)i 2 Br 5, and (e) ( i-pr DI)i 2 ( 6 6 ) 2. The region relevant to and aromatic stretches is highlighted. S15

16 4. yclic Voltammog grams Figure S28. yclic voltammogram for 4 (0.2 M [n-bu 4 ][PF 6 ] supporting electrolyte in TF, glassy carbon working electrode, 100 mv/ s scan rate). Scan beginss at the open circuit potential and proceeds in the anodic direction. S16

17 4. XRD Data RYSTAL DATA AD DATA OLLETIO PARAMETERS FOR (DI): formula formula weight space group P -1 (o. 2) a, Å (5) b, Å (9) c, Å (14), deg (4), deg (4), deg (4) V, Å (2) Z 2 d calc, g cm crystal dimensions, mm 0.70x0.25x0.20 temperature, K 150. radiation (wavelength, Å ) Mo K ( ) monochromator graphite linear abs coef, mm absorption correction applied empirical a transmission factors: min, max 0.95, 0.99 diffractometerr onius KappaD h, k, l range 0 to to to 23 2 range, deg mosaicity, deg 0.60 programs used SELXTL F data collected unique data 7163 R int ***** data used in refinement 7163 cutoff used in R-factor calculations F 2 o >2.0 (F 2 o ) data with I>2.0 (I) 4054 number of variables 371 largest shift/esd in final cycle 0.00 R(F o ) R w (F 2 o ) goodness of fit a Otwinowski Z. & Minor, W. Methods Enzymol. 1996, S17

18 RYSTAL DATA AD DATA OLLETIO PARAMETERS FOR (DI)i 2 ( 6 6 ): i 2 formula i 2 formula weight space group R -3 (o. 148) ) a, Å (14) c, Å (10) V, Å (15) Z 18 d calc, g cm crystal dimensions, mm 0.20x0.10x0.05 temperature, K 150. radiation (wavelength, Å ) u K ( ) monochromator confocal opticss linear abs coef, mm absorption correction applied empirical a transmission factors: min, max 0.72, 0.93 diffractometerr Rigaku RAPID-II h, k, l range 0 to to 0-17 to 17 2 range, deg mosaicity, deg 0.34 programs used SELXTL F data collected unique data 7320 R int ***** data used in refinement 7320 cutoff used in R-factor calculations F 2 o >2.0 (F 2 o ) data with I>2.0 (I) 5217 number of variables 443 largest shift/esd in final cycle 0.01 R(F o ) R w (F 2 o ) goodness of fit a Otwinowski Z. & Minor, W. Methods Enzymol. 1996, S18

19 RYSTAL DATA AD DATA OLLETIO PARAMETERS FOR (TF) 3 K(DI)i 2 ( 6 6 ): K 4 i 2 O 3, 2( 4 8 O) formula K 4 i 2 2O 5 formula weight space group P 1 21/n 1 (o. 14) a, Å (2) b, Å (4) c, Å (7), deg (10) V, Å (2) Z 4 d calc, g cm crystal dimensions, mm 0.90x0.60x0.36 temperature, K 150. radiation (wavelength, Å ) Mo K ( ) monochromator graphite linear abs coef, mm absorption correction applied empirical a transmission factors: min, max 0.43, 0.76 diffractometerr onius KappaD h, k, l range 0 to 16 0 to to 34 2 range, deg mosaicity, deg 0.62 programs used SELXTL F data collected unique data R int ***** data used in refinement cutoff used in R-factor calculations F 2 o >2.0 (F 2 o ) data with I>2.0 (I) 8653 number of variables 677 largest shift/esd in final cycle 0.00 R(F o ) R w (F 2 o ) goodness of fit a Otwinowski Z. & Minor, W. Methods Enzymol. 1996, S19

20 RYSTAL DATA AD DATA OLLETIO PARAMETERS FOR (DI)i 2 Br 2 : Br 2 4 i 2, 6 5 Br formula Br 3 4 i 2 formula weight space group P 1 2/c 1 (o. 13) a, Å (4) b, Å (2) c, Å (8), deg (10) V, Å (18) Z 4 d calc, g cm crystal dimensions, mm 0.72x0.48x0.24 temperature, K 150. radiation (wavelength, Å ) Mo K ( ) monochromator graphite linear abs coef, mm absorption correction applied empirical a transmission factors: min, max 0.03, 0.40 diffractometerr onius KappaD h, k, l range 0 to 23 0 to to 34 2 range, deg mosaicity, deg 1.17 programs used SELXTL F data collected unique data 9457 R int ***** data used in refinement 9457 cutoff used in R-factor calculations F 2 o >2.0 (F 2 o ) data with I>2.0 (I) 5505 number of variables 472 largest shift/esd in final cycle 0.00 R(F o ) R w (F 2 o ) goodness of fit a Otwinowski Z. & Minor, W. Methods Enzymol. 1996, S20

21 RYSTAL DATA AD DATA OLLETIO PARAMETERS FOR (DI)i 2 Br: Br 4 i 2, 0.5( 6 6 ) formula Br 4 i2 formula weight space group P -1 (o. 2) a, Å (6) b, Å (5) c, Å (8), deg (3), deg (3), deg (2) V, Å (3) Z 4 d calc, g cm crystal dimensions, mm 0.22x0.20x0.10 temperature, K 200. radiation (wavelength, Å ) u K ( ) monochromator confocal opticss linear abs coef, mm absorption correction applied empirical a transmission factors: min, max 0.44, 0.77 diffractometerr Rigaku RAPID-II h, k, l range 0 to to to 19 2 range, deg mosaicity, deg 0.54 programs used SELXTL F data collected unique data R int ***** data used in refinement cutoff used in R-factor calculations F 2 o >2.0 (F 2 o ) data with I>2.0 (I) number of variables 850 largest shift/esd in final cycle 0.00 R(F o ) R w (F 2 o ) goodness of fit a Otwinowski Z. & Minor, W. Methods Enzymol. 1996, S21

22 RYSTAL DATA AD DATA OLLETIO PARAMETERS FOR [(DI) 2 i 4 Br 5 ]PF 6 : Br 5 8 i 4 4, F 6 P, 2( O) formula Br 5 F 6 8 i 4 O 2P formula weight space group I 4 (o. 79) a, Å (2) c, Å (7) V, Å (2) Z 4 d calc, g cm crystal dimensions, mm 0.20x0.20x0.10 temperature, K 150. radiation (wavelength, Å ) u K ( ) monochromator confocal opticss linear abs coef, mm absorption correction applied empirical a transmission factors: min, max 0.28, 0.65 diffractometerr Rigaku RAPID-II h, k, l range -20 to to to 37 2 range, deg mosaicity, deg 0.39 programs used SELXTL F data collected unique data 7784 R int ***** data used in refinement 7784 cutoff used in R-factor calculations F 2 o >2.0 (F 2 o ) data with I>2.0 (I) 7382 number of variables 505 largest shift/esd in final cycle 0.00 R(F o ) R w (F 2 o ) goodness of fit absolute structure determination Flack parameter b (-0.03( 2)) a Otwinowski Z. & Minor, W. Methods Enzymol. 1996, b Flack,. D. Acta ryst., Sect. A 1983, A39, 876. S22

23 RYSTAL DATA AD DATA OLLETIO PARAMETERS FOR [(DI)i 2 (Me) 2 Br 2 ]PF 6 : Br 2 6 i 2, F 6 P, 0.833( 4 10 O) formula Br 2 F 6 6 i 2 O 0.83 P formula weight space group P 1 21/n 1 (o. 14) a, Å (3) b, Å (9) c, Å (5), deg (3) V, Å (3) Z 4 d calc, g cm crystal dimensions, mm 0.25x0.18x0.10 temperature, K 200. radiation (wavelength, Å ) u K ( ) monochromator confocal opticss linear abs coef, mm absorption correction applied empirical a transmission factors: min, max 0.32, 0.70 diffractometerr Rigaku RAPID-II h, k, l range 0 to 13 0 to to 19 2 range, deg mosaicity, deg 0.52 programs used SELXTL F data collected unique data 8415 R int ***** data used in refinement 8415 cutoff used in R-factor calculations F 2 o >2.0 (F 2 o ) data with I>2.0 (I) 7324 number of variables 574 largest shift/esd in final cycle 0.00 R(F o ) R w (F 2 o ) goodness of fit a Otwinowski Z. & Minor, W. Methods Enzymol. 1996, S23

24 5. omputational methods and optimized geometries omputational Methods. Geometry optimizations were performed using the Gaussian09 package. 1 The BP86 functional was employed with a 6-311G(d,p) basis set. Table S1. omparison of calculated and experimental (XRD) bond metrics. i i (DI)i 2 ( 6 6 ) (Expt.) 2.469(1) (DI)i 2 ( 6 6 ) (alc.) (TF) 3 K(DI)i 2 ( 6 6 ) (Expt.) (TF) 3 K(DI)i 2 ( 6 6 ) (alc.) (DI)i 2 Br 2 (Expt.) (7) (7) (7) (DI)i 2 Br 2 (alc.) (DI)i 2 Br (Expt.) 2.377(1) (9) (DI)i 2 Br (alc.) [(DI)i 2 (Me) 2 Br 2 ] + (Expt.) [(DI)i 2 (Me) 2 Br 2 ] + (alc.) 2.525(1) i 1 i (5) 1.965(4) (3) 2.015(3) (3) 1.922(3) (4) 1.969(4) 1.968(3) 1.959(3) (4) 2.052(3) i 2 i (3) 1.866(3) (3) 1.905(3) (4) 1.925(4) (3) 1.872(3) 1.881(2) 1.878(3) (4) 2.021(3) (6) 1.335(5) (4) 1.321(5) (6) 1.310(6) (5) 1.294(5) 1.298(5) 1.305(4) (6) 1.288(6) (7) 1.400(6) (4) 1.423(5) (5) 1.344(5) (6) 1.370(6) 1.358(6) 1.366(4) (6) 1.329(5) (6) 1.418(7) (5) 1.418(5) (5) 1.453(6) (6) 1.454(7) 1.451(4) 1.456(6) (6) 1.493(7) i 2.044(5) 2.025(5) 2.047(5) 2.028(5) (6) 1.951(7) 2.164(8) 2.170(7) 1.949(5) 2.198(4) i X (8) (8) (9) (7) (7) (6) (9) (9) (9) (9) Gaussian 09, Revision D.01, Frisch, M. J.; Trucks, G. W.; Schlegel,. B.; Scuseria, G. E.; Robb, M. A.; heeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; akatsuji,.; aricato, M.; Li, X.; ratchian,. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; ada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; asegawa, J.; Ishida, M.; akajima, T.; onda, Y.; Kitao, O.; akai,.; Vreven, T.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; eyd, J. J.; Brothers, E.; Kudin, K..; Staroverov, V..; Kobayashi, R.; ormand, J.; Raghavachari, K.; Rendell, A.; Burant, J..; Iyengar, S. S.; Tomasi, J.; ossi, M.; Rega,.; Millam,. J.; Klene, M.; Knox, J. E.; ross, J. B.; Bakken, V.; Adamo,.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; ammi, R.; Pomelli,.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; ioslowski, J.; Fox, D. J. Gaussian, Inc., Wallingford T, S24

25 Table S2. omparison of calculated and experimental (XRD) bond metrics for the bound 6 6 in complex 2. i i (DI)i 2 ( 6 6 ) (Expt.) (DI)i 2 ( 6 6 ) (alc.) 1 2, 2 3, 4 5, (1), 1.393(8), 1.39(1) ), 1.395(9) 1.425, 1.425, 1.425, , (7), 1.405(8) 1.434, (a) (b) (c) (d) Figure S29. Spin density plots (isovalue = 0.05) for (a) 3, (b) 4, (c) 5, and (d) 6. S25

26 Table S3. Relative energies for optimized structures (BP86/6-311G(d,p)) at different spin states. omplex (DI)i 2 Br 2 Spin State S = 0 (closed shell) Relative Energy 0 (DI)i 2 Br 2 S = 0 (open shell, anti-ferromagnetically coupled) +1.4 kcal (DI)i 2 Br 2 (DI)i 2 Br 2 [(DI)i 2 (Me) 2 Br 2 ] + [(DI)i 2 (Me) 2 Br 2 ] + S = 1 S = 2 S = 1/2 S = 3/ kcal +2.2 kcal +0.8 kcal 0 harge: 0 Multiplicity: 1 i i S

27 harge: 0 Multiplicity: 2 i i K O O O S

28 harge: 0 Multiplicity: 3 Br i S28

29 Br i harge: 0 Multiplicity: 1 (closed shell) Br i S

30 Br i harge: 0 Multiplicity: 1 (open shell, anti-ferromagnetically coupled) Br i S Br i

31 harge: 0 Multiplicity: 5 Br i S Br i harge: 0 Multiplicity: 2 Br i i

32 S harge: 1 Multiplicity: 4 Br i

33 Br i S harge: 1 Multiplicity: 2 Br i

34 Br i S34