Intramolecular frustrated lewis pair with the smallest boryl site: Reversible H2 addition and kinetic analysis

Angewandte Chemie - International Edition

Volumn 54, Issue 6, 2015, Pages 1749-1753

  Chernichenko, Konstantin ^a   Kátai, Bianka ^b   Pápai, Imre ^b   Zhivonitko, Vladimir ^c   Nieger, Martin ^a   Leskelä, Markku ^a   Repo, Timo ^a  

^a UNIVERSITY OF HELSINKI   (Finland)

^b INSTITUTE OF EXPERIMENTAL MEDICINE   (Hungary)

^c INTERNATIONAL TOMOGRAPHY CENTER   (Russian Federation)

Author keywords

Aminoboranes; Density functional calculations; Frustrated lewis pairs; Kinetics; Thermodynamics

Indexed keywords

DENSITY FUNCTIONAL THEORY; ENZYME KINETICS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; THERMODYNAMICS; THERMOMECHANICAL PULPING PROCESS;

AMINOBORANES; DFT CALCULATION; FRUSTRATED LEWIS PAIRS; KINETIC ANALYSIS; KINETIC FEATURES; LEWIS ACIDIC; SATURATION TRANSFER; VARIABLE-TEMPERATURE NMR;

KINETICS;

EID: 85027922926     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201410141     Document Type: Article

References (73)

1. For a comprehensive review on FLP chemistry, see: Topics in Current Chemistry (Eds.: G. Erker, D. W. Stephan), Springer, 2013, Vol. 332 and 334.
2. D. W. Stephan, S. Greenberg, T. W. Graham, P. Chase, J. J. Hastie, S. J. Geier, J. M. Farrell, C. C. Brown, Z. M. Heiden, G. C. Welch, M. Ullrich, Inorg. Chem. 2011, 50, 12338-12348;
3. J. Paradies, Angew. Chem. Int. Ed. 2014, 53, 3552 - 3557;
4. Angew. Chem. 2014, 126, 3624-3629.
5. G. C. Welch, R. R. S. Juan, J. D. Masuda, D.W. Stephan, Science 2006, 314, 1124-1126;
6. G. C. Welch, D.W. Stephan, J. Am. Chem. Soc. 2007, 129, 1880-1881;
7. P. Spies, G. Erker, G. Kehr, K. Bergander, R. Fröhlich, S. Grimme, D. W. Stephan, Chem. Commun. 2007, 5072-5074;
8. V. Sumerin, F. Schulz, M. Nieger, M. Leskelä, T. Repo, B. Rieger, Angew. Chem. Int. Ed. 2008, 47, 6001 - 6003;
9. Angew. Chem. 2008, 120, 6090-6092;
10. P. A. Chase, D.W. Stephan, Angew. Chem. Int. Ed. 2008, 47, 7433 - 7437;
11. Angew. Chem. 2008, 120, 7543-7547.
12. V. Sumerin, K. Chernichenko, M. Nieger, M. Leskelä, B. Rieger, T. Repo, Adv. Synth. Catal. 2011, 353, 2093-2110.
13. L. Greb, P. Oña-Burgos, B. Schirmer, S. Grimme, D. W. Stephan, J. Paradies, Angew. Chem. Int. Ed. 2012, 51, 10164 -10168;
14. Angew. Chem. 2012, 124, 10311-10315;
15. Y. Segawa, D.W. Stephan, Chem. Commun. 2012, 48, 11963-11965;
16. L. Greb, S. Tussing, B. Schirmer, P. Oña-Burgos, K. Kaupmees, M. Lokov, I. Leito, S. Grimme, J. Paradies, Chem. Sci. 2013, 4, 2788-2796;
17. L. J. Hounjet, C. Bannwarth, C. N. Garon, C. B. Caputo, S. Grimme, D. W. Stephan, Angew. Chem. Int. Ed. 2013, 52, 7492 - 7495;
18. Angew. Chem. 2013, 125, 7640-7643.
19. B. Inés, D. Palomas, S. Holle, S. Steinberg, J. A. Nicasio, M. Alcarazo, Angew. Chem. Int. Ed. 2012, 51, 12367 - 12369;
20. Angew. Chem. 2012, 124, 12533-12536;
21. J. A. Nicasio, S. Steinberg, B. Ines, M. Alcarazo, Chem. Eur. J. 2013, 19, 11016-11020;
22. L. Greb, C.-G. Daniliuc, K. Bergander, J. Paradies, Angew. Chem. Int. Ed. 2013, 52, 5876 - 5879;
23. Angew. Chem. 2013, 125, 5989-5992.
24. G. Ero s, H. Mehdi, I. Pápai, T. A. Rokob, P. Király, G. Tárkányi, T. Soós, Angew. Chem. Int. Ed. 2010, 49, 6559 - 6563;
25. Angew. Chem. 2010, 122, 6709-6713;
26. G. Eros, K. Nagy, H. Mehdi, I. Pápai, P. Nagy, P. Király, G. Tárkányi, T. Soós, Chem. Eur. J. 2012, 18, 574-585.
27. D. Chen, J. Klankermayer, Chem. Commun. 2008, 2130-2131;
28. D. Chen, Y. Wang, J. Klankermayer, Angew. Chem. Int. Ed. 2010, 49, 9475 - 9478
29. Angew. Chem. 2010, 122, 9665-9668;
30. G. Ghattas, D. Chen, F. Pan, J. Klankermayer, Dalton Trans. 2012, 41, 9026-9028;
31. Y. Liu, H. Du, J. Am. Chem. Soc. 2013, 135, 6810-6813;
32. S.Wei, H. Du, J. Am. Chem. Soc. 2014, 136, 12261-12264.
33. A. M. Chapman, M. F. Haddow, D. F.Wass, J. Am. Chem. Soc. 2011, 133, 8826-8829;
34. A. M. Chapman, D. F. Wass, Dalton Trans. 2012, 41, 9067-9072.
35. J. M. Farrell, J. A. Hatnean, D.W. Stephan, J. Am. Chem. Soc. 2012, 134, 15728-15731;
36. E. R. Clark, A. Del Grosso, M. J. Ingleson, Chem. Eur. J. 2013, 19, 2462-2466.
37. V. Sumerin, F. Schulz, M. Atsumi, C. Wang, M. Nieger, M. Leskelä, T. Repo, P. Pyykkö, B. Rieger, J. Am. Chem. Soc. 2008, 130, 14117-14119;
38. K. Chernichenko, M. Nieger, M. Leskelä, T. Repo, Dalton Trans. 2012, 41, 9029-9032; K. Chernichenko,
39. A. Madarász, I. Pápai, M. Nieger, M. Leskelä, T. Repo, Nat. Chem. 2013, 5, 718-723.
40. For some examples of using simple BX3 and RBX2 boranes in FLP chemistry, see:
41. T. Klatt, J. T. Markiewicz, C. Sämann, P. Knochel, J. Org. Chem. 2014, 79, 4253-4269, and references therein;
42. X. Zhao, D. W. Stephan, Chem. Commun. 2011, 47,1833-1835;
43. M. J. Sgro, J. Dömer, D.W. Stephan, Chem. Commun. 2012, 48, 7253-7255.
44. For a review on the Lewis acidity of boranes, see: I. B. Sivaev, V. I. Bregadze, Coord. Chem. Rev. 2014, 270 - 271, 75 - 88.
45. For instance, BH3 is predicted to be significantly less acidic than B(C6 F5)3 in our calculations (for details, see the Supporting Information).
46. 2; see: C. Jiang, O. Blacque, H. Berke, Organometallics 2009, 28, 5233-5239.
47. T. A. Rokob, A. Hamza, I. Pápai, J. Am. Chem. Soc. 2009, 131, 10701-10710.
48. Avery similar picture for the isomers of 1 could be observed by NMR spectroscopy in [D8]toluene as the solvent.
49. For details, see the Supporting Information.
50. The datively bound "head-to-tail" dimer of 1 has been identified computationally as well, but it is predicted to be very high in free energy (30 kcalmol-1 higher than trans-(1) 2).
51. M. Sajid, G. Kehr, T. Wiegand, H. Eckert, C. Schwickert, R. Pöttgen, A. J. P. Cardenas, T. H. Warren, R. Fröhlich, C. G. Daniliuc, G. Erker, J. Am. Chem. Soc. 2013, 135, 8882-8895.
52. S. Schwendemann, R. Fröhlich, G. Kehr, G. Erker, Chem. Sci. 2011, 2, 1842-1849;
53. K. V. Axenov, C. M. Mömming, G. Kehr, R. Fröhlich, G. Erker, Chem. Eur. J. 2010, 16, 14069-14073.
54. D. J. Parks, W. E. Piers, G. P. A. Yap, Organometallics 1998, 17, 5492-5503.
55. D. Feller,D. A. Dixon, K. A. Peterson, J. Phys. Chem. A 1998, 102, 7053-7059;
56. H.W. Smith,W. N. Lipscomb, J. Chem. Phys. 1965, 43, 1060-1064.
57. At higher temperatures, the two dimeric forms of 1 are indistinguishable; therefore, we refer to the reactant state of H2 activation as 1=2 (1)2 + H2.
58. A comparison of the measured and calculated reaction Gibbs free energies indicates that the present computational approach overestimates the thermodynamic stability of product 2 by approximately 2-3 kcalmol- 1 (see the Supporting Information).
59. Similar solvent effects have been previously reported for H2 activation with a norbornane-linked phosphorus/boron pair; see:
60. M. Sajid, A. Lawzer, W. Dong, C. Rosorius, W. Sander, B. Schirmer, S. Grimme, C. G. Daniliuc, G. Kehr, G. Erker, J. Am. Chem. Soc. 2013, 135, 18567-18574.
61. The reduced hydride affinity of 1 is partially due to dimerization. A detailed energy decomposition analysis for the two reactions is provided in the Supporting Information.
62. For a review on theoretical mechanistic studies on FLP-type H2 activation, see:
63. T. A. Rokob, I. Pápai, Top. Curr. Chem, 2013, 332, 157-211; for a recent contribution analyzing dynamic effects, see:
64. M. Pu, T. Privalov, ChemPhysChem 2014, 15, 2936-2944.
65. T. A. Rokob, I. Bakó, A. Stirling, A. Hamza, I. Pápai, J. Am. Chem. Soc. 2013, 135, 4425-4437.
66. For kinetic studies of the hydrogen activation by FLPs, see: A. Karkamkar, K. Parab, D. M. Camaioni, D. Neiner, H. Cho, T. K. Nielsen, T. Autrey, Dalton Trans. 2013, 42, 615-619, and Ref. [3a, 5c].
67. S. Forsén, R. A. Hoffman, J. Chem. Phys. 1963, 39, 2892-2901;
68. S. Forsén, R. A. Hoffman, J. Chem. Phys. 1964, 40, 1189-1196;
69. R. L. Jarek, R. J. Flesher, S. K. Shin, J. Chem. Educ. 1997, 74, 978-982.
70. For recent applications of SST NMR spectroscopy in studies of hydrogen exchange reactions, see:
71. M. Montag, J. Zhang, D. Milstein, J. Am. Chem. Soc. 2012, 134, 10325-10328;
72. W. Wang, T. B. Rauchfuss, L. Zhu, G. Zampella, J. Am. Chem. Soc. 2014, 136, 5773-5782.
73. V. V. Zhivonitko, V. V. Telkki, K. Chernichenko, T. Repo, M. Leskelä, V. Sumerin, I. V. Koptyug, J. Am. Chem. Soc. 2014, 136, 598-601.