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High Resolution Variable Pressure NMR for Chemical Kinetics

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High Pressure NMR

Part of the book series: NMR Basic Principles and Progress ((NMR,volume 24))

Abstract

In order to study chemical kinetics with any precision it is necessary to have good resolution similar to that accepted for normal analytical studies, and excellent control of temperature. We show how it has been possible to satisfy these two requirements with a high pressure probe constructed for use at the highest magnetic fields. The use of high pressure NMR is then illustrated by a series of specific examples which involve widely differing exchange rates and which embrace a range of rate constants varying over 18 orders of magnitude. The majority of the systems discussed are of solvent exchange on solvated cations, but an example of electron exchange and one of fluxional processes within a protein are also included. The examples illustrate well the unique understanding that knowledge of activation volumes gives to mechanistic processes and the inherent superiority of volume determinations over entropy determinations alone. The specific examples are followed by a more concise overall review of work in the field dealing with solvation complexes of a variety of geometries and with rate processes at pressure in the areas of bioinorganic, organometallic and organic chemistry.

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References

  1. Earl WL, Vanni H, Merbach AE (1978) J Magn Reson 30: 571

    CAS  Google Scholar 

  2. Vanni H, Earl WL, Merbach AE (1978) J Magn Reson 29: 11

    CAS  Google Scholar 

  3. Gaarz U, Lüdemann H-D (1979) Ber Bunsenges Phys Chem

    Google Scholar 

  4. Frey U, Helm L, Merbach AE (1990) High Pressure Research 2: 297

    Google Scholar 

  5. Rapaport I, Helm L, Merbach AE, Bernhard P, Ludi A (1988) Inorg Chem 27: 873

    CAS  Google Scholar 

  6. Bernhard P. Helm L, Ludi A, Merbach AE (1985) J Am Chem Soc 107: 312

    CAS  Google Scholar 

  7. Helm L, Elding LI, Merbach AE (1985) Inorg Chem 24: 1719

    CAS  Google Scholar 

  8. Gröning O, Drakenberg T, Elding LI (1982) Inorg Chem 21: 1820

    Google Scholar 

  9. Hugi-Cleary D, Helm L, Merbach AE (1985) Helv Chim Acta 68: 545

    CAS  Google Scholar 

  10. Akitt J (1989) Progress NMR Spectroscopy 21: 1

    Google Scholar 

  11. Merbach AE (1982) Pure & Appi Chem 54: 1479

    CAS  Google Scholar 

  12. Merbach AE (1987) Pure & Appi Chem 59: 161

    CAS  Google Scholar 

  13. Pittet P-A, Elbaze G, Helm L, Merbach AE (1990) Inorg Chem 29: 1936

    CAS  Google Scholar 

  14. Helm L, Ammann C, Merbach AE (1987) Zeitschrift Physikal Chem Neue Folge 155: 145

    CAS  Google Scholar 

  15. Frey U, Helm L, Merbach AE, Romeo R (1989) J Am Chem Soc 111: 8161

    CAS  Google Scholar 

  16. Frey U, Merbach AE (1990) High Pressure Research 5: 628

    Google Scholar 

  17. Frey U, Helm L, Merbach AE (1990) Helv Chim Acta 73: 199

    CAS  Google Scholar 

  18. Turin-Rossier M, Hugi-Cleary D, Merbach AE (1990) Inorg Chim Acta 167: 245

    CAS  Google Scholar 

  19. Turin-Rossier M, Hugi-Cleary D, Frey U, Merbach AE (1990) Inorg Chem 29: 1374

    CAS  Google Scholar 

  20. Newman KE, Meyer FK, Merbach AE (1979) J Am Chem Soc 101: 1470

    CAS  Google Scholar 

  21. Stebler M, Nielson RM, Siems WF, Hunt JP, Dodgen HW, Wherland S (1988) Inorg Chem 27: 2893

    CAS  Google Scholar 

  22. Cossy C, Barnes AC, Enderby JE, Merbach AE (1989) J Chem Phys 90: 3254

    CAS  Google Scholar 

  23. Cossy C, Merbach AE (1988) Pure & Appi Chem 60: 1785

    CAS  Google Scholar 

  24. Cossy C, Helm L, Merbach AE (1987) Inorg Chim Acta 139: 147

    CAS  Google Scholar 

  25. Cossy C, Helm L, Merbach AE (1988) Inorg Chem 27: 1973

    CAS  Google Scholar 

  26. Cossy C, Helm L, Merbach AE (1989) Inorg Chem 28: 2699

    CAS  Google Scholar 

  27. Wagner G (1980) FEBS Letters 112: 280

    CAS  Google Scholar 

  28. Moore P (1985) Pure & Appi Chem 57: 347

    CAS  Google Scholar 

  29. Ando I, Webb GA (1986) Magn Res Chem 24: 557

    CAS  Google Scholar 

  30. Ducommun Y, Merbach AE (1986) In: van Eldik R (ed) Inorganic high pressure chemistry, Chap 2. Elsevier, Amsterdam, p 69

    Google Scholar 

  31. Jonas J (1987) In: van Eldik R, Jonas J (eds) High pressure chemistry and biochemistry, D Reidel, Dordrecht, p 193

    Google Scholar 

  32. Merbach AE (1987) In: van Eldik R, Jonas J (eds) High pressure chemistry and biochemistry, D Reidel, Dordrecht, p. 311

    Google Scholar 

  33. van Eldik R (1987) In: van Eldik R, Jonas J (eds) High pressure chemistry and biochemistry, D Reidel, Dordrecht, p 333

    Google Scholar 

  34. Kotowski M, van Eldik R (1989) Coord Chem Rev 93: 19

    CAS  Google Scholar 

  35. van Eldik R, Asano T, LeNoble WJ (1989) Chem Rev 89: 549

    Google Scholar 

  36. Ammann C, Moore P, Merbach AE, McAteer CH (1980) Helv Chim Acta 63: 268

    CAS  Google Scholar 

  37. Hugi-Cleary D, Helm L, Merbach AE (1987) J Am Chem Soc 109: 4444

    CAS  Google Scholar 

  38. Hugi AD, Helm L, Merbach AE (1987) Inorg Chem 26: 1763

    CAS  Google Scholar 

  39. Hugi AD, Helm L, Merbach AE (1985) Helv Chim Acta 68: 508

    CAS  Google Scholar 

  40. Swaddle TW, Merbach AE (1981) Inorg Chem 20: 4212

    CAS  Google Scholar 

  41. Carle DL, Swaddle TW (1975) Can J Chem 51: 3795

    Google Scholar 

  42. Meyer FK, Monnerat AR, Newman KE, Merbach AE (1982) Inorg Chem 21: 774

    CAS  Google Scholar 

  43. Dellavia I (1990) PhD Thesis, University of Lausanne

    Google Scholar 

  44. Rapaport I, Laurenczy G, Zbinden D, Merbach AE (to be submitted)

    Google Scholar 

  45. Ducommun Y, Zbinden D, Merbach AE (1982) Helv Chim Acta 65: 1385

    CAS  Google Scholar 

  46. Ducommun Y, Newman KE, Merbach AE (1979) Helv Chim Acta 62: 2511

    CAS  Google Scholar 

  47. Ducommun Y, Earl WL, Merbach AE (1979) Inorg Chem 18: 2754

    CAS  Google Scholar 

  48. Ducommun Y, Newman KE, Merbach AE (1980) Inorg Chem 19: 3696

    CAS  Google Scholar 

  49. Earl WL, Meyer FK, Merbach AE (1977) Inorg Chim Acta 25: 91

    Google Scholar 

  50. Meyer FK, Newman KE, Merbach AE (1979) Inorg Chem 18: 2142

    CAS  Google Scholar 

  51. Meyer FK, Newman KE, Merbach AE (1979) J Am Chem Soc 101: 5588

    CAS  Google Scholar 

  52. Helm L, Lincoln SF, Merbach AE, Zbinden D (1986) Inorg Chem 25: 2550

    CAS  Google Scholar 

  53. Yano Y, Fairhurst MT, Swaddle TW (1980) Inorg Chem 19: 3267

    CAS  Google Scholar 

  54. Sisley MJ, Yano Y, Swaddle TW (1982) Inorg Chem 21: 1141

    CAS  Google Scholar 

  55. Monnerat AR, Moore P. Newman KE, Merbach AE (1981) Inorg Chim Acta 47: 139

    CAS  Google Scholar 

  56. Ishii M, Funahashi S, Ishihara K, Tanaka M (1989) Bull Chem Soc Japan 62: 1852

    CAS  Google Scholar 

  57. Cossy C, Helm L, Merbach AE (1987) Helv Chim Acta 70: 1516

    CAS  Google Scholar 

  58. Moore P, Fielding L (1988) J Chem Soc Chem Comn 49

    Google Scholar 

  59. Ishii M, Funahashi S, Tanaka M (1987) Chem Letters 871

    Google Scholar 

  60. Batstone Cunningham RL, Dodgen HW, Hunt JP (1982) Inorg Chem 21: 3831

    Google Scholar 

  61. Ishii M, Funahashi S, Tanaka M (1988) Inorg Chem 27: 3192

    CAS  Google Scholar 

  62. Kuroiwa Y, Harada M, Tomiyasu H, Fukutomi H (1988) Inorg Chim Acta 146: 7

    CAS  Google Scholar 

  63. Harada M, Ikeda Y, Tomiyasu H, Fukutomi H (1984) Chem Letters 1195

    Google Scholar 

  64. Merbach AE, Vanni H (1977) Helv Chem Acta 60: 1124

    CAS  Google Scholar 

  65. Vanni H, Merbach AE (1979) Inorg Chem 18: 2758

    CAS  Google Scholar 

  66. Kessler J-E Knight CT, Merbach AE (1986) Inorg Chim Acta 115: 85

    Google Scholar 

  67. Knight CT, Merbach AE (1985) Inorg Chem 24: 576

    CAS  Google Scholar 

  68. Turin E, Nielson RM, Merbach AE (1987) Inorg Chim Acta 134: 79

    CAS  Google Scholar 

  69. Meyer FK, Earl WL, Merbach AE (1979) Inorg Chem 18: 888

    CAS  Google Scholar 

  70. Ducommun Y, Nichols P, Helm L, Elding LI, Merbach AE (1984) J Phys 45: C8 - 221

    Google Scholar 

  71. Ducommun Y, Helm, L Merbach AE, Hellquist B, Elding LI (1989) Inorg Chem 28: 377

    CAS  Google Scholar 

  72. Tubino M, Merbach AE (1983) Inorg Chim Acta 71: 149

    CAS  Google Scholar 

  73. Helm L, Elding LI, Merbach AE (1984) Helv Chim Acta 67: 1453

    CAS  Google Scholar 

  74. Berger J, Kotowski M, van Eldik R, Helm L, Frey U, Merbach AE (1989) Inorg Chem 28: 3759

    CAS  Google Scholar 

  75. Helm L, Merbach AE, Kotowski M, van Eldik R (1989) High pressure research 2: 49

    Google Scholar 

  76. Helm L, Meier P, Merbach AE, Tregloan PA (1983) Inorg Chim Acta 73: 1

    CAS  Google Scholar 

  77. Lincoln SF, Hounslow AM, Pisaniello DL, Doddridge BG, Coates JH, Merbach AE, Zbinden D (1984) Inorg Chem 23: 109

    Google Scholar 

  78. Lincoln SF, Hounslow AM, Doddridge BG, Coates JH, Merbach AE, Zbinden D (1985) Inorg Chim Acta 100: 207

    CAS  Google Scholar 

  79. Fielding L, Moore P (1989) J Chem Soc Dalton Trans 873

    Google Scholar 

  80. Pisaniello DL, Nichols PJ, Ducommun Y, Merbach AE (1982) Helv Chim Acta 65: 1025

    CAS  Google Scholar 

  81. Pisaniello DL, Helm L, Meier P, Merbach AE (1983) J Am Chem Soc 105: 4528

    CAS  Google Scholar 

  82. Ducommun Y, Helm L, Laurenczy G, Merbach AE (1989) Inorg Chim Acta 158: 3

    CAS  Google Scholar 

  83. Spiccia L, Swaddle TW (1985) J Chem Soc Chem Comm 67

    Google Scholar 

  84. Swaddle TW, Spiccia L (1986) Physica 139 & HOB: 684

    Google Scholar 

  85. Spiccia L, Swaddle TW (1987) Inorg Chem 26: 2265

    CAS  Google Scholar 

  86. Nielson RM, Dodgen HW, Hunt JP, Wherland S (1986) Inorg Chem 25: 582 231

    Google Scholar 

  87. Doine H, Swaddle TW (1988) Inorg Chem 27: 665

    CAS  Google Scholar 

  88. Doine H, Yano Y, Swaddle TW (1989) Inorg Chem 28: 2319

    CAS  Google Scholar 

  89. Doine H, Swaddle TW (1988) Can J Chem 66: 2763

    CAS  Google Scholar 

  90. Kirchner K, Dodgen HW, Wherland S, Hunt JP (1989) Inorg Chem 28: 604

    CAS  Google Scholar 

  91. Merbach AE, Moore P, Newman KE (1980) J Magn Reson 41: 30

    CAS  Google Scholar 

  92. Nielson RM, Hunt JP, Dodgen HW, Wherland S (1986) Inorg Chem 25: 1964

    CAS  Google Scholar 

  93. Morishima I, Ogawa S, Yamada H (1979) J Am Chem Soc 101: 7074

    CAS  Google Scholar 

  94. Morishima I, Ogawa S, Yamada H (1980) Biochemistry 19: 1569

    CAS  Google Scholar 

  95. Morishima I, Hara M (1983) Biochemistry 22: 4102

    CAS  Google Scholar 

  96. Morishima I, Hara M (1983) J Biological Chem 23: 14428

    Google Scholar 

  97. Morishima I, Hara M (1984) Biochemical and Biophysical Research Communications 121: 229

    CAS  Google Scholar 

  98. Roe DC (1985) J Magn Reson 63: 388

    CAS  Google Scholar 

  99. Van der Velde DG, Jonas J (1987) J Magn Reson 71: 480

    Google Scholar 

  100. Heaton B, Jonas J, Eguchi T, Hoffman G (1981) J Chem Soc Chem Comm 331

    Google Scholar 

  101. Heaton B, Strona L, Jonas J, Eguchi T, Hoffman G (1982) J Chem Soc Dalton Trans 1159

    Google Scholar 

  102. Krusic PJ, Jones DJ, Roe DC (1986) Organometallics 5: 456

    CAS  Google Scholar 

  103. Roe DC (1987) Organometallics 6: 942

    CAS  Google Scholar 

  104. Marder TB, Roe DC, Milstein D (1988) Organometallics 7: 1451

    CAS  Google Scholar 

  105. Batstone Cunningham RL, Dodgen HW, Hunt JP, Roundhill D (1983) J Chem Soc Dalton Trans 1473

    Google Scholar 

  106. Batstone Cunningham RL, Dodgen HW, Hunt JP, Roundhill D (1985) J Organomet Chem 289: 431

    Google Scholar 

  107. Ioset J, Helm L, Merbach AE, Roulet R, Grepioni F, Braga D (1988) Helv Chim Acta 71: 1458

    Google Scholar 

  108. Róthlisberger-Stebler M, Hummel W, Pittet P-A, Bürgi HB, Ludi A, Merbach AE (1988) Inorg Chem 27: 1358

    Google Scholar 

  109. Le Noble WJ, Bitterman S, Staub P, Meyer FK, Merbach AE (1979) J Org Chem 44: 3263

    Google Scholar 

  110. Le Noble WJ, Merbach AE, Schulman EM (1981) J Org Chem 46: 3352

    Google Scholar 

  111. Schulman EM, Merbach AE, Le Noble WJ (1982) J Org Chem 47: 431

    CAS  Google Scholar 

  112. Schulman EM, Merbach AE, Turin-Rossier M, Wedinger R, Le Noble WJ (1983) J Am Chem Soc 105: 3988

    CAS  Google Scholar 

  113. Isaacs NS, Rzepa HS, Sheppard RN, Lobo AM, Prabhakar S, Merbach AE (1987) J Chem Soc Perkin Trans 1477

    Google Scholar 

  114. Schulman EM, Cheung CK, Merbach AE, Yamada H, Le Noble WJ (1987) J Am Chem Soc 109: 7206

    CAS  Google Scholar 

  115. Jonas J, Xie C-L, Jonas A, Grandinetti PJ, Campbell D, Driscoll D (1988) Proc NAS 85: 4115

    CAS  Google Scholar 

  116. Artaki I, Sinha S, Irwin AD, Jonas J (1985) J Non-Cryst Solids 72: 391

    CAS  Google Scholar 

  117. Ohtani E, Taulelle F, Angelí AC (1985) Nature 314: 78

    CAS  Google Scholar 

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© 1990 Springer-Verlag, Berlin Heidelberg

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Merbach, A.E., Akitt, J.W. (1990). High Resolution Variable Pressure NMR for Chemical Kinetics. In: Jonas, J. (eds) High Pressure NMR. NMR Basic Principles and Progress, vol 24. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-75926-0_5

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  • DOI: https://doi.org/10.1007/978-3-642-75926-0_5

  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-642-75928-4

  • Online ISBN: 978-3-642-75926-0

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