Supporting Information:

Transcription

1 Supporting Information: ESI-MS Studies and Calculations on 2 nd Generation Grubbs and on Hoveyda-Grubbs thenium Olefin Metathesis Catalysts Hao-Yang Wang a, Wai-Leung Yim b, Yin-Long Guo a, and Jürgen O. Metzger c * a Shanghai Mass Spectrometry Center, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Lingling Road 345, Shanghai, China. b Institute of High Performance Computing, 1 Fusionopolis Way, #16-16 Connexis, Singapore , Singapore. c Institut für Reine und Angewandte Chemie, Carl von Ossietzky Universität Oldenburg, Carl-von-Ossietzky-Str. 9-11, Oldenburg, Germany. To whom correspondence should be addressed. Prof. Dr. Jürgen O. Metzger, Phone: +49/441/ , Fax: +49/441/ , Juergen.Metzger@uni-oldenburg.de 1

2 Contents 1. ESI-MS and ESI-MS/MS spectra 1.1. Fragmentation (Schemes S1-S4) 1.2. Table S Figures Spectra of 2 (Figure S2-S14) Spectra of 3 (Figure S15-S16) Spectra of 4-6 (Figure S17-S24) 2. Computational results 2.1. Tables S2 S Figures Compound 2 (Figure S25-28) Compounds 5 and 6 (Figure S29-36) 3. References Page

3 1. ESI-MS and ESI-MS/MS spectra 1.1. Fragmentation (Schemes S1-S4) Scheme S1. Proposed dissociation pathways of 4 + at m/z 600 PCy 3 O m/z 600 H & PCy 3 O m/z 522 P + m/z PCy 3 H m/z 281 P O m/z 404 Scheme S2. Proposed dissociation pathways of 5 + at m/z 626. m/z 406 m/z 442 O m/z 626 m/z 305 O m/z 548 O m/z 512 Scheme S3. Proposed dissociation pathways of 6 + at m/z 597. H m/z 307 m/z 444 H + or + H m/z 118 m/z 597 m/z 561 3

4 Scheme S4. Proposed dissociation pathways of 2 M + and of 2a M + (M=Li, a, K, Cs). + M Ph - H ---, M=Li m/z 555, M=a m/z 571, M=K m/z 665, M=Cs - PCy 3 - PCy 3 Ph - M Ph M + Ph PCy 3 M + [2a-] + at m/z M + m/z 855, M=Li m/z 871, M=a - CH 2 -Ph m/z 887, M=K - CH 3 -Ph - M m/z 981, M=Cs - CH 3 -Ph M + or m/z H m/z 405 Ph PCy 3 [2-] + at m/z 813 m/z 497 Ph M + M + - H m/z 575, M=Li m/z 591, M=a m/z 607, M=K m/z 701, M=Cs m/z 484, M=Li m/z 500, M=a m/z 516, M=K m/z 610, M=Cs m/z 483, M=Li m/z 499, M=a m/z 515, M=K m/z 609, M=Cs m/z 447, M=Li m/z 463, M=a m/z 479, M=K m/z 573, M=Cs 4

5 1.2. Table S1 Table S1. MS/MS result of 2a M + (M=Li, a, K, Cs). Product ions (m/z) Precursor ions -M/ -[M +C 7 H 8 -[M - [H (m/z) -C 7 H 7 / C 7 H 8 -[M +C 7 H 8 ] H +H] +H] +C 7 H 8 ] 2a Li + (575) 533/ / a a + (591) 533/ / a K + (607)) ---/ / a Cs + (701) ---/ / The main fragment ion series of 2a M + were formed by loss of toluene (C 7 H 8, -92 u) and [C 7 H 8 +H] (-128 u) when M = Li, or benzyl radical (C 7 H 7, -91 u) and [C 7 H 8 +H] (-128 u) with M = a, K, Cs. Interestingly, the ratios of these two kinds of main fragment ions [2a M ] and [2a M + -91/92] showed a clear trend: (a) 1.36; (b) 1.29; (c) 0.93; (d) 0.37, from Li + to a + to K + and finally to Cs +. Moreover, some other fragment pathways were observed, Such as: 2a. Li + eliminates Li (-42 u) to ion at m/z 533 and [Li+H] (-78 u) to ion at m/z 497; 2a. a + eliminates H (-36 u) to ion at m/z 555 and a (-58 u) to ion at m/z 533, whereas 2a. K + and 2a. Cs + eliminate H to ions at m/z 571 and m/z 665, respectively. (Figure S4) 5

6 1.3. Figures Figure S1. On-line micro-reactor devise for analysis of the alkali metal adduct ions of -catalysts Spectra of 2 (Figure S2-S14) Figure S2. ESI-MS/MS spectra for CID of ions: (a) Cy 3 P H + at m/z 281; (b) Cy 3 PCH + 3 at m/z 295; (c) H 2 IMes H + at m/z

7 Figure S3. ESI mass spectra of 2 with (a) Li; (b) a; (c) K; (d) Cs. Figure S4. ESI-MS/MS spectra for CID of: (a) 2a Li + at m/z 575; (b) 2a a + at m/z 591; (c) 2a K + at m/z 607; (d) 2a Cs + at m/z 701 (collision energy 6 ev). 7

8 Figure S5. (a) Isotopic pattern of the ion 2 Li + ; (b) theoretical isotopic pattern of 2 Li +. The alkali metal coordination with catalyst 2 is an equilibrium process, thus still some 2 +. were observed in low intensity (marked with * ). Figure S6. (a) Isotopic pattern of the ion 2a Li + ; (b) theoretical isotopic pattern of 2a Li +. Figure S7. (a) Isotopic pattern of the ion [2-] + ; (b) theoretical isotopic pattern of [2-] +. 8

9 Figure S8. (a) Isotopic pattern of the ion [2a-] + ; (b) theoretical isotopic pattern of [2a-] +. Figure S9. (a) Isotopic pattern of the ion 2 2 Li + ; (b) theoretical isotopic pattern of 2 2 Li +. Figure S10. (a) Isotopic pattern of the ion 2 K + ; (b) theoretical isotopic pattern of 2 K +. 9

10 Figure S11. (a) Isotopic pattern of the ion 2a K + ; (b) theoretical isotopic pattern of 2a K +. Figure S12. (a) Isotopic pattern of the ion (2) 2 K + ; (b) theoretical isotopic pattern of (2) 2 K +. Figure S13. ESI MS/MS spectrum for CID of: (a) [2a-] + at m/z

11 Figure S14. ESI-MS/MS spectrum of (2) 2 K + at m/z

12 Spectra of 3 (Figure S15-S16) Figure S15. (a) ESI-MS spectrum of catalyst 3 in CH 2 2 ; (b) ESI-MS/MS spectrum for CID of molecular ion 3 + at m/z 792. Figure S16. (a) ESI mass spectrum of catalyst 3 with added Li; (b) ESI-MS/MS spectrum for CID of [3-] + at m/z 757; (c) ESI-MS/MS spectrum for CID of 3 Li + at m/z 799; (d) ESI-MS/MS spectrum for CID of 3a Li + at m/z

13 Spectra of 4-6 (Figure S17-S24) Figure S17. ESI mass spectra of complexes (a) 4; (b) 5; (c) 6 dissolved in CH 2 2. Figure S18. ESI-MS/MS spectra for CID of: (a) 4 + at m/z 600; (b) 5 + at m/z 626; (c) 6 + at m/z

14 Figure S19. ESI mass spectra of (a) 4; (b) 5; (c) 6.with added Li. Figure S20. ESI-MS/MS spectra for CID of: (a) 4 Li + at m/z 607; (b) 5 Li + at m/z 633; (c) 6 Li + at m/z 604 (collision energy 12 ev). 14

15 Figure S21. ESI mass spectra of (a) 4; (b) 5; (c) 6.with added K. Figure S22. ESI-MS/MS spectra for CID of: (a) 4 K + at m/z 639; (b) 5 K + at m/z 665; (c) 6 K + at m/z 636 (collision energy 14 ev). 4. Li + gave the fragment ions at m/z 455 and at m/z 419 by elimination of [C 10 H 14 O+H 2 ] with152u and of [C 10 H 14 O+H 2 +H] with 188u and 4. K + gave the fragment ions at m/z

16 and at m/z 451 by elimination of the same neutrals. The same fragment ions at m/z 441, 447 and 483 from 5 Li + and 2a Li + could be observed, as well as in the case of 5 K + and 2a K + with the same fragment ions at m/z 441, 479 and 516. Elimination of [M + H] was observed in the fragmentation of 5 M + to ion at m/z 555. Figure S23. ESI-MS/MS spectra for CID of: (a) (6) 2 Li + at m/z 1201; (b) (6) 2 a + at m/z 1217; (c) (6) 2 K + at m/z 1233; (d) (6) 2 Cs + at m/z

17 Figure S24. ESI-MS/MS spectra for CID of: (a) 6 + at m/z 597; (b) 6 Li + at m/z 604; (c) 6 a + at m/z 620; (d) 6 K + at m/z 636; (e) 6 Cs + at m/z

18 2. Computational results Tables S2 S10 Table S2. Summary of energy for the discussed species Species Energy Species Energy 2 Li K a Li a a K PCy [2-] H 2 IMes [2-H 2 IMes] Li K Li K Li Li K K Table S3. Structural parameters of optimized structures of 2, 2 Li + and 2 K + (in parentheses X-ray diffraction data of 2 [1] ). Structural parameters 2 2 Li + 2 K + - (1) (Å) 2.49 (2.39) (2) (Å) 2.50 (2.40) C(H 2 IMes) (Å) 2.05 (2.09) P (Å) 2.54 (2.42) =C (Å) 1.86 (1.84) (1) -- (2) (degree) (167.7) C(H 2 IMes)--P (degree) (163.7) M + - (2) (Å) (2) -M + (degree)

19 Table S4. Structural parameters of optimized structures of 2a, 2a Li + and 2a K +. Structural parameters 2a 2a Li + 2a K + - (1) (Å) (2) (Å) C(H 2 IMes) (Å) =C (Å) (1) -- (2) (degree) M + - (2) (Å) (2) -M + (degree) Table S5. Structural parameters of the optimized structures of 5, 5a, 5 M + and 5a M + (in parentheses X-ray diffraction data of 5 [2] ). Structural parameters 5 5a 5 Li + 5 K + 5a Li 5a K + - (1) (Å) 2.43 (2.32) (2) (Å) 2.44 (2.34) C(H 2 IMes) (Å) 1.97 (1.98) O (Å) 2.29 (2.26) =C (Å) 1.86 (1.83) (1) -- (2) (degree) (156.5) C(H 2 IMes)--O (degree) (172.6) M + -O (Å) M + - (2) (Å) (2) -M + (degree)

20 Table S6. Structural parameters of the optimized structures of 6, 6a, 6 M + and 6a M + (in parentheses X-ray diffraction data of 6 [3] ). Structural parameters 6 6a 6 Li + 6 K + 6a Li + 6a K + - (1) (Å) 2.48 (2.37) (2) (Å) 2.47 (2.40) C(H 2 IMes) (Å) 2.04 (2.05) (Å) 2.14 (2.14) =C (Å) 1.84 (1.82) (1) -- (2) (degree) (164.4) C(H 2 IMes)--P (2) (170.2) (degree) M + - (Å) M + - (2) (Å) (2) -M + (degree) Table S7. The bond distances the alkali metal cations M + (M=Li or K) to the benzene carbon of H 2 IMes. Structural parameters 2 Li + 2 K + M + -C (1) (Å) M + -C (2) (Å) M + -C (3) (Å) M + -C (4) (Å) M + -C (5) (Å) M + -C (6) (Å) M 2 PCy 3 f a e b d c 20

21 Table S8. Bond distances the alkali metal cations M + (M=Li or K) to the carbons of benzylidene in 2a Li + and 2a K +. Structural parameters 2a Li + 2a K + M + -C (a) (Å) M + -C (b) (Å) M + -C (c) (Å) M + -C (d) (Å) M + -C (e) (Å) M + -C (f) (Å) M + f a e b d c Table S9. Structural parameters for optimized structure of [2-] +. Structural parameters [2-] + - (Å) C(H 2 IMes) (Å) P (Å) 2.58 =C (Å) 1.86 C(H 2 IMes)--P (degree)

22 Table S10. The bond distances of K + to the benzene carbons in 5 K +. Structural parameters 5 K + M + -C (1) (Å) 3.78 M + -C (2) (Å) 3.27 M + -C (3) (Å) 3.28 M + -C (4) (Å) 3.85 M + -C (5) (Å) 4.31 M + -C (6) (Å) 4.31 M + -C (7) (Å) 3.09 M + -C (8) (Å) 3.31 M + -C (9) (Å) 3.70 M + -C (10) (Å) 4.62 M + -C (11) (Å) 5.13 M + -C (12) (Å) 4.88 M + -C (13) (Å) K O

23 2.2. Figures Compound 2 (Figure S25-28) Figure S25. Optimized structure of 2. Figure S26. Optimized structure of [2-] +. 23

24 Figure 27. Optimized structure of 2 K +. Figure 28. Optimized structure of 2a K +. 24

25 Compounds 5 and 6 (Figure S29-36) Figure S29. Optimized structure of 5. Figure S30. Optimized structure of 5a. 25

26 Figure S31 Optimized structure of 5. K +. Figure S32. Optimized structure of 5a. K +. 26

27 Figure S33. Optimized structure of 6. Figure S34. Optimized structure of 6a. 27

28 Figure S35. Optimized structure of 6. K +. Figure S36. Optimized structure of 6a. K +. 28

29 3. Reference: 1. Love, J. A.; Sanford, M. S.; Day, M. W.; Grubbs, R. H. J. Am. Chem. Soc. 2003, 125, Garber, S. B.; Kingsbury, J. S.; Gray, B. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2000, 122, Ung, T.; Hejl, A.; Grubbs, R. H.; Schrodi, Y. Organometallics 2004, 23,