Supporting Information for the Paper Entitled, Terminal Titanyl Complexes of Tri- and Tetrametaphosphate:

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1 Supporting Information for the aper Entitled, Terminal Titanyl Complexes of Tri- and Tetrametaphosphate: Synethesis, Structures, and Reactivity with Hydrogen eroxide Julia M. Stauber, and Christopher C. Cummins Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts Contents 1 Spectroscopic characterization of Ti(IV) metaphosphate complexes. S3 1.1 [N] 4 [Ti 4 12 ] 2 ([N] 4 [1]) S3 1.2 [N] 2 [Ti 3 9 (acac)] ([N] 2 [2]) S9 1.3 [N] 4 [ 2 Ti 4 12 ] 2 ([N] 4 [3]) S [N] 2 [ 2 Ti 3 9 (acac)] ([N] 2 [4]) S21 2 Variable Temperature 31 { 1 H} NMR spectra of [N] 2 [2]. S27 3 Evaluating the water stability of [N] 2 [2]. S solution NMR spectrum of [N] 2 [2]. S29 5 Monitoring the conversion of [N] 4 [1] to [N] 4 [3] by UV-Vis spectroscopy. S31 To whom correspondence should be addressed S1

2 6 Monitoring the conversion of [N] 2 [2] to [N] 2 [4] by UV-Vis spectroscopy. S32 7 Monitoring the conversion of [N] 4 [1] to [N] 4 [3] by 31 NMR spectroscopy at 5 C. S33 8 ESI-MS( ) data displaying exchange of the titanyl oxygen of [N] 2 [2] with 18 H 2 and 17 H 2. S34 9 Treatment of [N] 4 [1] with 16 H 2 and 17 H 2. S H S H S38 1 Assessing the reversibility of the reaction of [N] 4 [1] with H 2. S4 11 xygen atom transfer (AT) from [N] 4 [3] to (Me) 3, h 3, and SMe 2. S (Me) S h S SMe S43 12 xygen atom transfer (AT) from [N] 2 [4] to h 3. S45 13 Experiments testing the catalytic activity of 1 and 2 towards organic substrates in the presence of H 2 2. S46 14 Experiments testing the oxidizing capacity of 3 and 4 towards organic substrates. S5 15 Crystallographic information for [N] 4 [1], [N] 2 [2], [N] 4 [3], and [N] 2 [4]. S X-ray crystal structure determination details S53 S2

3 1 Spectroscopic characterization of Ti(IV) metaphosphate complexes. 1.1 [N] 4 [Ti 4 12 ] 2 ([N] 4 [1]) N Figure S1: 31 { 1 H} NMR spectrum of [N] 4 [1] (CD 3 CN, 162 MHz, 25 C). S3

4 acetone CD 3 CN N + H Figure S2: 1 H NMR spectrum of [N] 4 [1] (CD 3 CN, 4 MHz, 25 C). S4

5 CD 3 CN CD 3 CN N + acetone Figure S3: 13 C{ 1 H} NMR spectrum of [N] 4 [1] (CD 3 CN, 11 MHz, 25 C). S5

6 Transmittance [%] Wavenumber (cm -1 ) 1 5 Figure S4: ATR-IR of [N] 4 [1]. Transmittance [%] Ti Ti Wavenumber (cm 1 ) Figure S5: Zoomed-in ATR-IR of [N] 4 [1]. S6

7 1 Wavenumber (cm -1 ) ε (M -1 cm -1 ) 6 Ti Ti Wavelength (nm) Figure S6: UV-Vis spectrum of [N] 4 [1] (.5 mm, MeCN, 2 C). S7

8 [Ti 4 12 ] A [Ti H + ] m/z B m/z m/z Figure S7: ESI-MS( ) of [N] 4 [1]. A: Zoomed-in spectrum; B: simulated spectrum (MeCN, 32 V). S8

9 1.2 [N] 2 [Ti 3 9 (acac)] ([N] 2 [2]) N Figure S8: 31 { 1 H} NMR spectrum of [N] 2 [2] (CD 3 CN, 162 MHz, 25 C). S9

10 Ti 2 CD 3 CN N + H Figure S9: 1 H NMR spectrum of [N] 2 [2] (CD 3 CN, 4 MHz, 25 C). S1

11 CD 3 CN CD 3 CN N + Ti Figure S1: 13 C{ 1 H} NMR spectrum of [N] 2 [2] (CD 3 CN, 11 MHz, 25 C). S11

12 Transmittance [%] Wavenumber (cm -1 ) Figure S11: ATR-IR of [N] 2 [2] Transmittance [%] Ti Wavenumber (cm -1 ) Figure S12: Zoomed-in ATR-IR of [N] 2 [2]. S12

13 12 Wavenumber (cm -1 ) ε (M -1 cm -1 ) Ti Wavelength (nm) Figure S13: UV-Vis spectrum of [N] 2 [2] (1. mm, MeCN, 2 C). S13

14 [Ti 3 9 ] A m/z 3.82 B m/z m/z Figure S14: ESI-MS( ) of [N] 2 [2]. A: Zoomed-in spectrum; B: simulated spectrum (MeCN, 32 V). The acac ligand is not observable under ESI-MS( ) conditions. S14

15 1.3 [N] 4 [ 2 Ti 4 12 ] 2 ([N] 4 [3]) [ 2 Ti 4 12] 2 N Figure S15: 31 { 1 H} NMR spectrum of [N] 4 [3] (CD 3 CN, 162 MHz, 25 C). S15

16 CD 3 CN N + H 2 Et 2 Et Figure S16: 1 H NMR spectrum of [N] 4 [3] (CD 3 CN, 4 MHz, 25 C). S16

17 MeCN MeCN N Figure S17: 13 C{ 1 H} NMR spectrum of [N] 4 [3] (CD 3 CN, 11 MHz, 25 C). S17

18 Transmittance [%] Wavenumber (cm -1 ) Figure S18: ATR-IR of [N] 4 [3]. Transmittance [%] Ti Ti Wavenumber (cm -1 ) Figure S19: Zoomed-in ATR-IR of [N] 4 [3]. S18

19 Wavenumber (cm -1 ) ε (M -1 cm -1 ) Ti Ti Wavelength (nm) Figure S2: UV-Vis spectrum of [N] 4 [3] (.5 mm, MeCN, 2 C). S19

20 [ 2 Ti 4 12 ] A m/z B m/z m/z Figure S21: ESI-MS( ) of [N] 4 [3]. A: Zoomed-in spectrum; B: simulated spectrum (MeCN, 32 V). S2

21 1.4 [N] 2 [ 2 Ti 3 9 (acac)] ([N] 2 [4]) N Figure S22: 31 { 1 H} NMR spectrum of [N] 2 [4] (CD 3 CN, 162 MHz, 25 C). S21

22 CD 3 CN 2 Ti overlapping with CD 3 CN overlapping with CD 3 CN N + THF Et 2 acetone H 2 THF Et Figure S23: 1 H NMR spectrum of [N] 2 [4] (CD 3 CN, 4.1 MHz, 25 C). S22

23 CD 3 CN CD 3 CN 2 N + Ti Et 2 Et Figure S24: 13 C{ 1 H} NMR spectrum of [N] 2 [4] (CD 3 CN, 11 MHz, 25 C). S23

24 Transmittance [%] Wavenumber (cm -1 ) Figure S25: ATR-IR of [N] 2 [4]. Transmittance [%] Ti Wavenumber (cm -1 ) Figure S26: Zoomed-in ATR-IR of [N] 2 [4]. S24

25 12 Wavenumber (cm -1 ) ε (M -1 cm -1 ) 8 6 Ti Wavelength (nm) Figure S27: UV-Vis spectrum of [N] 2 [4] (1. mm, MeCN, 2 C). S25

26 [ 2 Ti 3 9 ] - A m/z B m/z m/z Figure S28: ESI-MS( ) of [N] 2 [4]. A: Zoomed-in spectrum; B: simulated spectrum (MeCN, 32 V). The acac ligand is not observable under ESI-MS( ) conditions. S26

27 2 Variable Temperature 31 { 1 H} NMR spectra of [N] 2 [2]. A solution of [N] 2 [2] (1 mg) was prepared in MeCN (.5 ml). An initial 31 { 1 H} NMR spectrum of the sample was collected (25 C), and then the temperature of the NMR probe was cooled in increments of 1 C until a final temperature of 35 C was reached. 31 { 1 H} NMR spectra were collected every 1 C, and the temperatures were calibrated with methods reported by Merbach et al o C 15 o C 5 o C -5 o C -15 o C -25 o C -35 o C Figure S29: Variable temperature 31 { 1 H} NMR spectra of [N] 2 [2] collected between 25 and 35 C (MeCN, 22.4 MHz). S27

28 3 Evaluating the water stability of [N] 2 [2]. A colorless solution of [N] 2 [2] (1 mg,.68 mmol, 1. eq) was prepared in MeCN (.5 ml) and transferred to an NMR tube. To this solution was added H 2 (1 µl,.55 mmol, 82 eq) via 1 µl syringe, and a 31 { 1 H} NMR spectrum was immediately collected. To the same sample was added an additional 1 µl H 2 (2 µl total,.11 mmol total, 16 eq), and a 31 { 1 H} NMR spectrum was immediately collected, and then collected again after 24 h (Figure S3). There were no changes observed in the 31 { 1 H} NMR spectra after the H 2 additions N Figure S3: 31 { 1 H} NMR spectrum of a sample of [N] 2 [2] in the presence of 16 eq H 2 after 24 h (MeCN, 162 MHz, 25 C). S28

29 4 17 solution NMR spectrum of [N] 2 [2]. A colorless solution of [N] 2 [2] (15 mg,.1 mmol, 1. eq) was prepared in MeCN (.5 ml) and transferred to an NMR tube. To this solution was added 7% 17 H 2 (1 µl,.55 mmol, 55 eq). The tube was capped and inverted to effect good mixing. A 17 NMR spectrum (Figure S31) of this mixture was collected at 25 C. After the acquisition was complete, a 31 { 1 H} NMR spectrum was collected, indicating the [N] 2 [Ti 3 9 (acac)] complex remained intact in the presence of excess water during the course of the 17 NMR experiment H 2 [ 17 Ti 3 9 (acac)] Figure S31: 17 NMR spectrum of [N] 2 [2] spiked with 7% 17 H 2 (1 µl, 55 eq). Externally referenced to D 2 (68 MHz, MeCN, 25 C). S29

30 Figure S32: Zoomed-in 17 NMR spectrum of [N] 2 [2] spiked with 7% 17 H 2 (1 µl, 55 eq). Externally referenced to D 2 (68 MHz, MeCN, 25 C). S3

31 5 Monitoring the conversion of [N] 4 [1] to [N] 4 [3] by UV-Vis spectroscopy. A 1. mm solution of [N] 4 [Ti 4 12 ] 2 was prepared in acetonitrile (2 ml) and transferred to a 1 cm path length Quartz cuvette. An initial UV-Vis spectrum was acquired, and then to this colorless solution was added urea hydrogen peroxide (2 mg,.6 mmol, 3 eq) as a solid. The cuvette was shaken to effect good mixing, and UV-Vis spectra were acquired every 6 sec for a total of 2 h. Absorbance (AU) Wavenumber (cm -1 ) Ti Ti 4 Ti Ti Wavelength (nm) Figure S33: UV-Vis spectra displaying the conversion of [N] 4 [1] to [N] 4 [3] monitored over the course of 2 h (25 C, MeCN, 1. mm). S31

32 6 Monitoring the conversion of [N] 2 [2] to [N] 2 [4] by UV-Vis spectroscopy. A 1. mm solution of [N] 2 [2] was prepared in acetonitrile (2 ml) and transferred to a 1 cm path length Quartz cuvette. An initial UV-Vis spectrum was acquired, and then to this colorless solution was added 3% aqueous hydrogen peroxide (2 µl,.1 mmol, 6 eq) via 1 µl syringe. UV-Vis spectra were acquired every 3 sec for a total of 1 min. 2. Wavenumber (cm -1 ) Absorbance (AU) Ti Ti Wavelength (nm) Figure S34: UV-Vis spectra of 2 upon treatment with 3% H 2 2 collected every 3 sec over the course of 1 min (25 C, 1. M, MeCN). S32

33 7 Monitoring the conversion of [N] 4 [1] to [N] 4 [3] by 31 NMR spectroscopy at 5 C. A solution of [N] 4 [1] (1 mg,.34 mmol, 1. eq) was prepared in MeCN and transferred to an NMR tube. An initial 31 { 1 H} NMR spectrum was collected, and then the solution was frozen in a dry ice/acetone slush bath. While the solution was allowed to freeze, the NMR probe was cooled to 5 C. Solid UH (approx. 5 mg,.55 mmol, 16 eq) was then added on top of the frozen solution. The tube was capped, and then quickly inserted into the pre-cooled NMR probe. Spectra were collected every 4 min for a total of 76 min, and temperatures were calibrated with methods reported by Merbach et al. 1 Ti Ti 4 Ti Ti 4 initial 8 min 16 min 24 min 36 min 44 min 52 min 6 min 4 68 min Ti Ti min Figure S35: 31 { 1 H} NMR spectra of a solution of 1 treated with UH monitored over the course of 76 min at 5 C (MeCN, 22.4 MHz). S33

34 8 ESI-MS( ) data displaying exchange of the titanyl oxygen of [N] 2 [2] with 18 H 2 and 17 H 2. Two solutions of [N] 2 [2] (<1 mg per sample) were prepared in MeCN (2 ml). 18 H 2 (97% enriched, 5 µl) was injected into one solution and 17 H 2 (7% enriched, 1 µl) was injected into the other solution via 1 µl syringe. ESI-MS ( ) data for both solutions were immediately collected. [ 16 Ti 3 9 ] [ 18 Ti 3 9 ] m/z Figure S36: ESI-MS( ) of a sample of [N] 2 [2] spiked with 5 µl of 97% enriched 18 H 2 (MeCN, 32 V). [ 16 Ti 3 9 ] [ 17 Ti 3 9 ] m/z Figure S37: ESI-MS( ) of a sample of [N] 2 [2] spiked with 1 µl of 7% enriched 17 H 2 (MeCN, 32 V). S34

35 9 Treatment of [N] 4 [1] with 16 H 2 and 17 H H 2. To a colorless solution of [N] 4 [1] (15 mg,.5 mmol, 1. eq) in MeCN (.5 ml) was added ACS reagent grade H 2 (1 µl,.52 mmol, 1 eq) via 1 µl syringe. A 31 { 1 H} NMR spectrum of this solution was immediately collected (Figure S38). The sample was allowed to stand at ambient temperature (22 C) for an additional 24 h, at which point a 31 { 1 H} NMR spectrum was collected again (Figure S4) N Figure S38: 31 { 1 H} NMR spectrum of [N] 4 [1] after 1 min in the presence of 1 eq H 2 (MeCN, 162 MHz, 25 C). S35

36 A 2 A 2 'B 2 B 2 ' spin system A B = A ' B ' = 34.6 Hz A A ' = B B ' = 2.5 Hz Multiplet 1 δ Multiplet 2 δ Figure S39: Top: 31 { 1 H} NMR spectrum of [N] 4 [1] after 1 min in the presence of 1 eq H 2 (MeCN, MHz, 25 C). Bottom: 31 NMR spectrum displaying an A 2 A 2 B 2 B 2 splitting pattern 2 simulated using the program gnmr. 3 S36

37 N Figure S4: 31 { 1 H} NMR spectrum of [N] 4 [1] after 24 h in the presence of 1 eq H 2 (MeCN, 162 MHz, 25 C). S37

38 H 2. To a colorless solution of [N] 4 [1] (15 mg,.5 mmol, 1. eq) in MeCN (.5 ml) was added 7% enriched 17 H 2 (5 µl,.3 mmol, 5 eq) via 1 µl syringe. 17 and 31 { 1 H} NMR spectra of this solution were collected after 3 min (Figure S41). The sample was allowed to stand at ambient temperature (22 C) for an additional 24 h, at which point 17 and 31 { 1 H} NMR spectra were collected again (Figure S42) Figure S41: 17 NMR spectrum of [N] 4 [1] after 3 min in the presence of 5 eq 17 H 2 (externally referenced to D 2, MeCN, 68 MHz, 25 C). Inset: 31 { 1 H} NMR spectrum of the same solution (22.4 MHz). S38

39 * third species * * artifact at 1/2 spectral width Figure S42: 17 NMR spectrum of [N] 4 [1] after 24 h in the presence of 5 eq 17 H 2 (externally referenced to D 2, MeCN, 68 MHz, 25 C). Inset: 31 { 1 H} NMR spectrum of the same solution (22.4 MHz). S39

40 1 Assessing the reversibility of the reaction of [N] 4 [1] with H 2. To a colorless solution of [N] 4 [1] (15 mg,.5 mmol, 1. eq) in MeCN (.5 ml) was added ACS reagent grade H 2 (1 µl,.52 mmol, 1 eq) via 1 µl syringe. A 31 { 1 H} NMR spectrum of this solution was immediately collected (Figure S43, top). The contents of the NMR tube were then transferred to a 2 ml scintillation vial. The vial and its contents were heated at 8 C under vacuum for 2 h. The colorless residue was then dissolved in MeCN (.5 ml), and a 31 { 1 H} NMR spectrum (Figure S43, middle) of the resulting solution was collected. This procedure was repeated once more such that the sample was heated to 8 C under vacuum for a total of 5 h, at which point a final 31 { 1 H} NMR spectrum (Figure S43, bottom) of the residue was collected in MeCN (.5 ml). N + initial Ti * Ti 4 H 2, excess vacuum, 8 o C H 2 H Ti Ti 4 * 2 h under vac. at 8 o C * 5 h under vac. at 8 o C Figure S43: 31 { 1 H} NMR spectra of a solution of [N] 4 [1] after initial treatment with 1 eq H 2 (top), after the solution was heated to 8 C under vacuum for 2 h and redissolved in MeCN (middle), and after the solution was heated to 8 C under vacuum for 5 h and redissolved in MeCN (bottom). MeCN, 121 MHz, 25 C. S4

41 11 xygen atom transfer (AT) from [N] 4 [3] to (Me) 3, h 3, and SMe (Me) 3. To a MeCN (.4 ml) solution of [N] 4 [3] (1 mg,.34 mmol, 1. eq) in an NMR tube was added neat (Me) 3 (4 µl,.34 mmol, 1 eq) via 1 µl syringe. A 31 { 1 H} NMR spectrum of the reaction mixture was collected after 1 min N + [Ti 4 12 ] 2 4 (Me) 3 (Me) Figure S44: 31 { 1 H} NMR spectra of a solution of [N] 4 [3] after treatment with 1 eq (Me) 3 at 23 C after 1 min (MeCN, 121 MHz, 25 C). S41

42 11.2 h 3. To a MeCN (.4 ml) solution of [N] 4 [3] (1 mg,.34 mmol, 1. eq) in an NMR tube was added a solution of h 3 (4 mg,.1 mmol, 4 eq) in MeCN (.1 ml). A 31 { 1 H} NMR spectrum was collected immediately (Figure S45, top), and then again after 3 min (Figure S45, bottom) N + 4 [2Ti412]2 h 3 h [Ti 4 12 ] Figure S45: 31 { 1 H} NMR spectra of a solution of [N] 4 [3] after treatment with 4 eq h 3 at 23 C after 3 sec (top), and after 3 min (bottom). MeCN, 121 MHz, 25 C. S42

43 11.3 SMe 2. To a solution of [N] 4 [3] (1 mg,.34 mmol, 1. eq) in CD 3 CN (.5 ml) was added SMe 2 (2 µl,.3 mmol, 1 eq) via 1 µl syringe. 1 H (Figure S46) and 31 { 1 H} NMR (Figure S47) spectra were collected after 2 h of reaction time at 23 C SMe 2 MeCN N + SMe Figure S46: 1 H NMR spectrum of a solution of [N] 4 [3] after treatment with 1 eq SMe 2 at 23 C after 2 h (CD 3 CN, 4 MHz, 25 C). S43

44 N + [ 2 Ti 4 12 ] [Ti 4 12 ] Figure S47: Initial 31 { 1 H} NMR spectra of a solution of [N] 4 [3] (top), and 2 h after treatment with 1 eq SMe 2 at 23 C (bottom) (CD 3 CN, 4 MHz, 25 C). S44

45 12 xygen atom transfer (AT) from [N] 2 [4] to h 3. To a MeCN (.4 ml) solution of [N] 4 [4] (15 mg,.1 mmol, 1. eq) in an NMR tube was added a solution of h 3 (4 mg,.2 mmol, 1.5 eq) in MeCN (.1 ml). A 31 { 1 H} NMR spectrum was collected immediately (Figure S48, top), and then the tube was placed in a preheated oil bath set to 8 C. A 31 { 1 H} NMR spectrum of the sample was collected again after the reaction had been heated for 1 h at 7 C (Figure S48, bottom) N + h 3 [ 2 Ti 3 9 (acac)] h 3 [Ti 3 9 (acac)] Figure S48: 31 { 1 H} NMR spectra of a solution of [N] 2 [4] after treatment with 1.5 eq h 3 at 23 C after 3 sec (top), and after 1 h at 7 C (bottom) (MeCN, 121 MHz, 25 C). S45

46 13 Experiments testing the catalytic activity of 1 and 2 towards organic substrates in the presence of H 2 2. The conditions used for these reactions were adapted from literature procedures for similar transformations. 4 General procedure for phenol, cis-cyclooctene, and diphenylmethanol substrates: In the fumehood, colorless solutions of [N] 4 [1] (1 mg,.34 mmol, 1. eq) and [N] 2 [2] (1 mg,.68 mmol, 1. eq) were prepared in CD 3 CN (.5 ml). To these solutions was added each substrate (2 eq per Ti center). After allowing complete dissolution of the substrate, urea H 2 2 (2 eq per Ti center) was added to each solution as a solid. The colors of the solutions gradually became orange, and then 1 H and 31 { 1 H} NMR spectra of these reaction mixtures were collected after 2 min at 23 C. 1 H and 31 { 1 H} NMR spectra of the reaction mixtures were checked again after 2 additional h at 23 C. No new organic products were observed in the 1 H NMR spectra, so the solutions were heated at 7 C for 4 h and checked again. The 1 H NMR spectra did not contain resonances corresponding to any new organic products, and the 31 { 1 H} NMR spectra all displayed resonances associated with the peroxotitanium metaphosphate complexes 3 and 4. S46

47 N + [ 2 Ti 4 12 ] Figure S49: 31 { 1 H} NMR spectrum of the reaction of a solution of 1 + phenol + UH after heating at 7 C for 4 h (CD 3 CN, 121 MHz, 25 C) phenol acetone MeCN phenol N + urea water Figure S5: 1 H NMR spectrum of the reaction of a solution of 1 + phenol + UH after heating at 7 C for 4 h (CD 3 CN, 4 MHz, 25 C). nly urea, N + and phenol resonances are observed. S47

48 N + [ 2 Ti 4 12 ] Figure S51: 31 { 1 H} NMR spectrum of the reaction of a solution of 1 + diphenylmethanol + UH after heating at 7 C for 4 h (CD 3 CN, 121 MHz, 25 C) diphenylmethanol MeCN acetone N + diphenylmethanol urea water Figure S52: 1 H NMR spectrum of the reaction of a solution of 1 + diphenylmethanol + UH after heating at 7 C for 4 h (CD 3 CN, 4 MHz, 25 C). nly urea, N + and diphenylmethanol resonances are observed. S48

49 N + [ 2 Ti 4 12 ] Figure S53: 31 { 1 H} NMR spectrum of the reaction of a solution of 1 + cis-cyclooctene + UH after heating at 7 C for 4 h (CD 3 CN, 121 MHz, 25 C) MeCN acetone ciscyclooctene N + ciscyclooctene urea ciscyclooctene Figure S54: 1 H NMR spectrum of the reaction of a solution of 1 + cis-cyclooctene + UH after heating at 7 C for 4 h (CD 3 CN, 4 MHz, 25 C). nly urea, N + and cis-cyclooctene resonances are observed. S49

50 14 Experiments testing the oxidizing capacity of 3 and 4 towards organic substrates. General procedure for phenol, cis-cyclooctene, and diphenylmethanol substrates: In the fumehood, orange solutions of [N] 4 [3] (1 mg,.34 mmol, 1. eq) and [N] 2 [4] (1 mg,.68 mmol, 1. eq) were prepared in CD 3 CN (.5 ml). To these solutions was added each substrate (1 eq per Ti center). 1 H and 31 { 1 H} NMR spectra of these reaction mixtures were collected after 2 min at 23 C. 1 H and 31 { 1 H} NMR spectra of the reaction mixtures were checked again after 2 additional h at 23 C. No new organic products were seen in the 1 H NMR spectra, so the solutions were heated at 7 C for 4 h. 1 H NMR analyses of these reaction mixtures after heating did not show the presence of any new organic products, and the 31 { 1 H} NMR spectra all displayed resonances associated with the peroxotitanium metaphosphate complexes 3 and MeCN phenol N + phenol water Figure S55: 1 H NMR spectrum of the reaction of a solution of 3 + phenol after heating at 7 C for 4 h (CD 3 CN, 4 MHz, 25 C). nly N + and phenol resonances are observed. S5

51 diphenylmethanol MeCN diphenylmethanol N + diphenylmethanol water Figure S56: 1 H NMR spectrum of the reaction of a solution of 3 + diphenylmethanol after heating at 7 C for 4 h (CD 3 CN, 4 MHz, 25 C). nly N + and diphenylmethanol resonances are observed. S51

52 ciscyclooctene MeCN N + cis- cyclooctene ciscyclooctene Figure S57: 1 H NMR spectrum of the reaction of a solution of 3 + cis-cyclooctene after heating at 7 C for 4 h (CD 3 CN, 4 MHz, 25 C). nly N + and cis-cyclooctene resonances are observed. S52

53 15 Crystallographic information for [N] 4 [1], [N] 2 [2], [N] 4 [3], and [N] 2 [4] X-ray crystal structure determination details. Low-temperature (1 K) diffraction data (φ and ω) were collected on a Bruker-AXS X8 Kappa Duo diffractometer coupled to a Smart AEX2 CCD detector with Mo Kα radiation (λ =.7173 Å) from an IµS micro-source. Absorption and other corrections were applied using SADABS. 5 The structures were solved by direct methods using SHELXT 6 and refined against F 2 on all data by full-matrix least squares with SHELXL using established refinement approaches. 8 All hydrogen atoms were included into the model at geometrically calculated positions and refined using a riding model. The isotropic displacement parameters of all hydrogen atoms were fixed to 1.2 times the U eq value of the atoms they are linked to (1.5 times for methyl groups). Details about crystal properties, diffraction data and crystal structures can be found in the tables below. All disorders were refined with the help of similarity restraints on 1,2- and 1,3-distances as well as similar AD and advanced rigid bond restraints. 9 The program SQUEEZE 1 as implemented in LATN 11 was used to account for the contribution of disordered solvent contained in voids within the crystal lattice for structures [N] 2 [1], [N] 4 [3], and [N] 2 [4]. The solvent contribution was added to the model in a separate file (the.fab file) by SHELXL. S53

54 1 4 3 Ti1 4a 2a 1 1 Ti a 3a 5 2a Ti1a 1 1a 3b Figure S58: Solid-state structures of [Ti 4 12 ] 2 4 (1, left) and [Ti 3 9 (acac)] 2 (2, right) rendered with LATN 12 with thermal ellipsoids at the 5% probability level, and with [N] + cations and solvent molecules of crystallization omitted for clarity. Selected interatomic distances (Å) and angles ( ): 1, Ti (13), Ti (12), Ti (13), Ti1-4a (13), Ti1-5a 2.14(13), Ti1-Ti1a 4.233(9), Σ( eq -Ti- eq ) 341.8(9); 2, Ti (2), Ti (2), Ti (18), Ti (19), Ti (19), Ti (19), Σ( eq -Ti- eq ) 355.8(2) b Ti1 2a Ti a 3a 1b Ti1b 2a 3 3 1b 2b Figure S59: Solid-state structures of [ 2 Ti 4 12 ] 2 4 (3, left) and [ 2 Ti 3 9 (acac)] 2 (4, right) rendered with LATN 12 with thermal ellipsoids at the 5% probability level, and with [N] + cations and solvent molecules of crystallization omitted for clarity. Selected interatomic distances (Å) and angles ( ): 3, Ti (8), Ti (8), Ti (13), Ti (12), Ti1-3b 1.986(13), Ti1-4a 1.963(12), (6), Ti1-Ti1b 4.23(1), Σ( eq -Ti- eq ) 352.(7); 4, Ti (4), Ti (5), Ti (3), Ti (2), Ti (2), Ti (2), Ti (2), (6), Σ( eq -Ti- eq ) 353.9(8). 4 S54

55 Table 1: Crystallographic Data for [N]4[1], and [N]2[2] [N]4[1] [N]2[2] Reciprocal Net code / CCDC X8_14143 / X8_14116 / Empirical formula, FW (g/mol) C38.5H34N1.574Ti.5, C77H67N2127Ti, Color / Morphology Colorless / Block Colorless / Block Crystal size (mm 3 ) Temperature (K) 1(2) 1(2) Wavelength (Å) Crystal system, Space group Triclinic, 1 Monoclinic, 21 Unit cell dimensions (Å, ) a = (11), α = (1) a = 1.714(2), α = 9 b = (11), β = (1) b = (2), β = 1.945(4) c = (12), γ = (1) c = (5), γ = 9 Volume (Å 3 ) (5) (12) Z 4 2 Density (calc., g/cm 3 ) Absorption coefficient (mm 1 ) F() Theta range for data collection ( ) 1.38 to to Index ranges 21 h 21, 21 k 21, 15 h 15, 18 k 18, 22 l l 39 Reflections collected Independent reflections, Rint 1888, ,.484 Completeness to θmax (%) Absorption correction Semi-empirical from equiv. Semi-empirical from equiv. Refinement method Full-matrix least-squares on F 2 Full-matrix least-squares on F 2 Data / Restraints / arameters 1888 / 1488 / / 1489 / 894 Goodness-of-fit a Final R indices b [I > 2σ(I)] R1 =.382, wr2 =.993 R1 =.376, wr2 =.845 R indices b (all data) R1 =.459, wr2 =.147 R1 =.494, wr2 =.895 Largest diff. peak and hole (e Å 3 ) and and.49 a GooF = Σ[w(F 2 o F c 2 ) 2 ] (n p) b R 1 = Σ F o Fc Σ Fo ; wr2 = Σ[w(F 2 o F c 2 ) 2 Σ[w(F o 2 ) 2 ] 1 ; w = σ 2 (F o 2 )+(a) 2 +b ; = 2F2 c +max(f o 2,) 3 S55

56 Table 2: Crystallographic Data for [N]4[3], and [N]2[4] [N]4[3] [N]2[4] Reciprocal Net code / CCDC X8_14131 / X8_14133 / Empirical formula, FW (g/mol) C156H138N12816Ti2, C77H67N2137Ti, Color / Morphology range / Needle range / Block Crystal size (mm 3 ) Temperature (K) 1(2) 1(2) Wavelength (Å) Crystal system, Space group Triclinic, 1 Monoclinic, 21 Unit cell dimensions (Å, ) a = (4), α = (5) a = (17), α = 9 b = (4), β = (4) b = (19), β = 1.464(3) c = (4), γ = (4) c = (4), γ = 9 Volume (Å 3 ) (17) 37.2(1) Z 1 2 Density (calc., g/cm 3 ) Absorption coefficient (mm 1 ) F() Theta range for data collection ( ) to to Index ranges 2 h 2, 2 k 2, 13 h 13, 16 k 16, 21 l l 34 Reflections collected Independent reflections, Rint 1672, ,.479 Completeness to θmax (%) Absorption correction Semi-empirical from equiv. Semi-empirical from equiv. Refinement method Full-matrix least-squares on F 2 Full-matrix least-squares on F 2 Data / Restraints / arameters 1672 / 1927 / / 1814 / 968 Goodness-of-fit a Final R indices b [I > 2σ(I)] R1 =.381, wr2 =.172 R1 =.332, wr2 =.755 R indices b (all data) R1 =.452, wr2 =.1125 R1 =.396, wr2 =.787 Largest diff. peak and hole (e Å 3 ).857 and and.296 a GooF = Σ[w(F 2 o F c 2 ) 2 ] (n p) b R 1 = Σ F o Fc Σ Fo ; wr2 = Σ[w(F 2 o F c 2 ) 2 Σ[w(F o 2 ) 2 ] 1 ; w = σ 2 (F o 2 )+(a) 2 +b ; = 2F2 c +max(f o 2,) 3 S56

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58 (8) Müller,. ractical Suggestions for Better Crystal Structures. Crystallogr. Rev. 29, 15, (9) Thorn, A.; Dittrich, B.; Sheldrick, G. M. Enhanced Rigid-bond Restraints. Acta Crystallogr. A 212, 68, (1) van der Sluis,.; Spek, A. L. BYASS: An Effective Method for the Refinement of Crystal Structures Containing Disordered Solvent Regions. Acta Crystallogr. A 199, 46, (11) Spek, A. L. Structure Validation in Chemical Crystallography. Acta Crystallogr. D 29, 65, (12) Spek, A. L. author. Acta Cryst. 29, D65, S58