Supporting information for the article

Transcription

1 Supporting information for the article S1 Exceptional behavior of Ni 2 O 2 species revealed by ESI-MS and MS/MS studies in solution. Application of superatomic core to facilitate new chemical transformations Dmitry B. Eremin and Valentine P. Ananikov,, * Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Pr. 47, Moscow , Russia; val@ioc.ac.ru Department of Chemistry, Saint Petersburg State University, Stary Petergof, , Russia. CONTENTS Ni(acac) 2 solution prepared in a plastic tube from another vendor... S2 Spectral change upon heating and storage of the Ni(acac) 2 solution... S3 Spectral study with varying ESI parameters... S4 Relative intensity dependence of the collision energy curves in MS/MS mode... S5 Monometallic nickel species and coordination of small molecular ligands studied with ESI- MS and MS/MS experiments... S7 ESI-MS/MS spectra of target ions... S8 Experimental and calculated spectra of studied ions... S12 1 H NMR spectra of test solutions... S21 1 H NMR spectrum of a solvent from the plastic tube... S22

2 S2 Ni(acac) 2 solution prepared in a plastic tube from another vendor Figure S1. ESI-MS spectra of Ni(acac) 2 solution in acetonitrile prepared under standard conditions in plastic tube from another vendor (with contaminant signals marked by blue symbols); m/z = range (glass syringes were used for dilution). Position and intensity of contaminant-containing signals may vary from one type of plastic to another (cf. Figure 1 in the article), while the presence of many peaks due to influence of contaminants or impurities is clearly visible. The changes in the relative intensities of nickel acetylacetonate species were also noticeable.

3 S3 Spectral change upon heating and storage of the Ni(acac) 2 solution To determine the influence of sample preparation conditions and estimate stability of the solutions we conducted a series of experiments. The solution was studied at the room temperature (Figure S1A), heated at 70 C in an oil bath for 2 h and 4 h (Figure S1B, S1C) and was left at room temperature for one week (Figure S1D). Detected nickel ions corresponded to [Ni(acac) 2 + Na] +, [Ni 2 (acac) 3 ] +, [Ni 2 (acac) 4 + Na] +, and [Ni 3 (acac) 5 ] +, respectively (acac = C 5 H 7 O 2 ). Indeed the ions corresponding to the monometallic, bimetallic and trimetallic nickel species were detected in all the cases, and bimetallic ion possessed the highest intensity. However, comparing the spectra we can see the change of the relative intensity of the detected ions. After equilibration for one week binuclear complex was the major signal in slotuion. The observed picture suggests that appearance of the ions is connected with initial solution and may not be completely attributed to generation of the ions under ESI conditions. Figure S2. ESI-MS spectrum of the solution immediately after preparation (A), spectrum of the solution after two hours heating at 70 C (B), spectrum of the solution after four hours heating at 70 C (C), and spectrum of the solution after a week at room temperature (D).

4 Spectral study with varying ESI parameters Instrumental settings such as end plate offset (shield voltage), capillarity (capillary voltage), and dry gas temperature have been shown to influence the ionization of analyte in ESI-MS. The effects of these parameters were specified by varying the drying gas temperature from 100 to 300 C, capillary voltage from 6000 V to -500 V, and shield voltage from 1000 V to 100 V. Obtained results did not show noticeable changes depending on instrumental settings that did not disapprove the possibility of the ions formation directly in the solution. S4

5 S5 Relative intensity dependence of the collision energy curves in MS/MS mode Intens., % m/z Ni(acac) m/z Ni(acac)(H 2O) m/z Ni(acac)(N 2) m/z Ni(acac)(H 2O) 2 m/z Ni(acac)(CH 3CN) m/z Ni(acac)(CH 3CN) (H 2O) Applied collision energy, ev Figure S3. Energy dependences of the product ions abundances for the [Ni(acac)(CH 3 CN)] + derived from ESI-MS/MS with CID experiments. Intens., % 100 m/z m/z Ni 2 (acac) 3 (C 3H 4O) Ni 2 (acac) 2 (OH) 80 m/z m/z Ni 2 (acac)(c H O) Ni 2 (acac) 2 (CO) m/z Ni 2 (acac) 2 (C 5H 6O 2) m/z Ni 2 (acac) 2 m/z Ni 2 (acac) 2(C 3H 5O) m/z Ni 2 (acac) Applied collision energy, ev Figure S4. Energy dependences of the product ions abundances for the [Ni 2 (acac) 3 ] + derived from ESI-MS/MS with CID experiments.

6 Intens., % m/z NaNi(acac) 2 m/z NaNi 2 (acac) 4 S Applied collision energy, ev Figure S5. Energy dependences of the product ions abundances for the [Ni 2 (acac) 4 +Na] + derived from ESI-MS/MS with CID experiments. Intens., % m/z Ni 2 (acac) 3 m/z Ni 2 (acac) 4(C 3H 4O) m/z Ni 3 (acac) Applied collision energy, ev Figure S6. Energy dependences of the product ions abundances for the [Ni 3 (acac) 5 ] + derived from ESI-MS/MS with CID experiments.

7 Monometallic nickel species and coordination of small molecular ligands studied with ESI-MS and MS/MS experiments S7 Figure S7. ESI-MS spectrum of Ni(acac) 2 solution in CH 3 CN (m/z range). Figure S8. ESI-MS/MS spectrum of [Ni(acac)(CH 3 CN)] +. Experimental MS (top) and calculated MSs (bottom). Here and later means the mass center of fragmentation region.

8 S8 ESI-MS/MS spectra of target ions Figure S9. Experimental ESI-MS/MS spectrum of [Ni(acac) 2 +Na] + (applied collision energy 8 ev). Figure S10. ESI-MS/MS spectrum of [Ni 2 (acac) 3 ] + (applied collision energy 40 ev).

9 Figure S11. ESI-MS/MS spectrum of [Ni 2 (acac) 4 +Na] + (applied collision energy 12 ev). S9

10 Figure S12. ESI-MS/MS spectrum of [Ni 3 (acac) 5 ] + (applied collision energy 8 ev). S10

11 Figure S13. ESI-MS/MS spectrum of [Ni(acac)(CH 3 CN)] + (applied collision energy 14 ev). S11

12 S12 Experimental and calculated spectra of studied ions Figure S14. Expanded ESI-MS spectrum of individual ion (Ni(acac) 2 solution in CH 3 CN). Experimental MS (top) and [Ni(acac) 2 +Na] + calculated MS (bottom). Figure S15. Expanded ESI-MS spectrum of individual ion (Ni(acac) 2 solution in CH 3 CN). Experimental MS (top) and [Ni 2 (acac) 3 ] + calculated MS (bottom).

13 S13 Figure S16. Expanded ESI-MS spectrum of individual ion (Ni(acac) 2 solution in CH 3 CN). Experimental MS (top) and [Ni 2 (acac) 4 +Na] + calculated MS (bottom). Figure S17. Expanded ESI-MS spectrum of individual ion (Ni(acac) 2 solution in CH 3 CN). Experimental MS (top) and [Ni 3 (acac) 5 ] + calculated MS (bottom). Figure S18. Expanded ESI-MS/MS spectrum of individual ion ([Ni 3 (acac) 5 ] + fragmentation). Experimental MS (top) and [Ni 2 (acac) 4 C 3 H 3 O] + calculated MS (bottom).

14 S14 Figure S19. Expanded ESI-MS/MS spectrum of individual ion ([Ni 2 (acac) 3 ] + fragmentation). Experimental MS (top) and [NiC 2 H 3 ] + calculated MS (bottom). Figure S20. Expanded ESI-MS/MS spectrum of individual ion ([Ni 2 (acac) 3 ] + fragmentation). Experimental MS (top) and [NiC 3 H 5 ] + and [NiC 2 HO] + calculated MS (bottom). Figure S21. Expanded ESI-MS/MS spectrum of individual ion ([Ni 2 (acac) 3 ] + fragmentation). Experimental MS (top) and [NiC 2 H 5 O] + calculated MS (bottom).

15 S15 Figure S22. Expanded ESI-MS/MS spectrum of individual ion ([Ni 2 (acac) 3 ] + fragmentation). Experimental MS (top) and [NiC 3 H 3 O] + calculated MS (bottom). Figure S23. Expanded ESI-MS/MS spectrum of individual ion ([Ni 2 (acac) 3 ] + fragmentation). Experimental MS (top) and [NiC 4 H 3 O 2 ] + calculated MS (bottom). Figure S24. Expanded ESI-MS/MS spectrum of individual ion ([Ni 2 (acac) 3 ] + fragmentation). Experimental MS (top) and [NiC 5 H 7 O 2 ] + calculated MS (bottom).

16 S16 Figure S25. Expanded ESI-MS/MS spectrum of individual ion ([Ni 2 (acac) 3 ] + fragmentation). Experimental MS (top) and [Ni(N 2 )(C 4 H 3 O 2 )] + calculated MS (bottom). Figure S26. Expanded ESI-MS/MS spectrum of individual ion ([Ni 2 (acac) 3 ] + fragmentation). Experimental MS (top) and [Ni(H 2 O)(C 5 H 7 O 2 )] + calculated MS (bottom). Figure S27. Expanded ESI-MS/MS spectrum of individual ion ([Ni 2 (acac) 3 ] + fragmentation). Experimental MS (top) and [Ni 2 (O)(C 5 H 7 O 2 )] + calculated MS (bottom).

17 S17 Figure S28. Expanded ESI-MS/MS spectrum of individual ion ([Ni 2 (acac) 3 ] + fragmentation). Experimental MS (top) and [Ni 2 (acac)c 3 H 4 O] + calculated MS (bottom). Figure S29. Expanded ESI-MS/MS spectrum of individual ion ([Ni 2 (acac) 3 ] + fragmentation). Experimental MS (top) and [Ni 2 (acac)c 4 H 6 O] + calculated MS (bottom). Figure S30. Expanded ESI-MS/MS spectrum of individual ion ([Ni 2 (acac) 3 ] + fragmentation). Experimental MS (top) and [Ni 2 (acac)c 5 H 6 O] + and [Ni 2 (acac) 2 ] + calculated MS (bottom).

18 S18 Figure S31. Expanded ESI-MS/MS spectrum of individual ion ([Ni 2 (acac) 3 ] + fragmentation). Experimental MS (top) and [Ni 2 (acac) 2 HO] + calculated MS (bottom). Figure S32. Expanded ESI-MS/MS spectrum of individual ion ([Ni 2 (acac) 3 ] + fragmentation). Experimental MS (top) and [Ni 2 (acac) 2 CO] + calculated MS (bottom). Figure S33. Expanded ESI-MS/MS spectrum of individual ion ([Ni 2 (acac) 3 ] + fragmentation). Experimental MS (top) and [Ni 2 (acac) 2 C 3 H 5 O] + calculated MS (bottom).

19 S19 Figure S34. Expanded ESI-MS spectrum of individual ion (Ni(acac) 2 solution in CH 3 CN). Experimental MS (top) and [Ni(acac)] + calculated MS (bottom). Figure S35. Expanded ESI-MS spectrum of individual ion (Ni(acac) 2 solution in CH 3 CN). Experimental MS (top) and [Ni(acac)N 2 ] + calculated MS (bottom). Figure S36. Expanded ESI-MS spectrum of individual ion (Ni(acac) 2 solution in CH 3 CN). Experimental MS (top) and [Ni(acac)(CH 3 CN)] + calculated MS (bottom).

20 S20 Figure S37. Expanded ESI-MS spectrum of individual ion (Ni(acac) 2 solution in CH 3 CN). Experimental MS (top) and [Ni(acac)(CH 3 CN)(H 2 O)] + calculated MS (bottom). Figure S38. Expanded ESI-MS spectrum of individual ion (Ni(acac) 2 solution in CH 3 CN). Experimental MS (top) and [Ni(acac) 2 +H] + calculated MS (bottom).

21 1 H NMR spectra of test solutions The samples with known composition and concentration were used to estimate the detection limit of the NMR spectrometer (Figures S39 and S40). The signals of acetylacetone were detected in the case of 10-3 mg dissolved in 0.6 ml of the solvent. S21 Figure S39. 1 H NMR spectrum (600 MHz) of acetylacetone in CDCl 3. Figure S40. Characteristic region of the 1 H NMR spectrum (600 MHz, 230 scans) of 10-3 mg of acetylacetone in 0.6 ml of CDCl 3 (sample preparation was done by dilution).

22 S22 1 H NMR spectrum of a solvent from the plastic tube No signals of significant intensity were detected. CH 3 CN H 2 O ppm Figure S41. 1 H NMR spectrum (600 MHz, 1000 scans) of d 3 -acetonitrile from plastic tube (tube with 0.6 ml of solvent was shaken for 30 minutes).