The impact of ion pair association upon the 1H NMR spectra of cationic complexes akin to Grubbs catalysts

Magnetic Resonance in Chemistry

Volumn 48, Issue 4, 2010, Pages 261-269

  Schiemenz, G̈unter Paulus ^a  

^a UNIVERSITY OF KIEL   (Germany)

Author keywords

1H; Cyclophanes; Enantiotopicity; Ion pairs; Molecular prisms; NMR; Ruthenium complexes

Indexed keywords

IONS; METAL COMPLEXES; NUCLEAR MAGNETIC RESONANCE; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; RUTHENIUM COMPOUNDS;

1H; CATIONIC COMPLEXES; CATIONICS; CYCLOPHANES; ENANTIOTOPICITY; GRUBBS CATALYSTS; H NMR SPECTRA; ION PAIRS; MOLECULAR PRISM; RUTHENIUM COMPLEXES;

TRANSITION METALS;

EID: 77949843521     PISSN: 07491581     EISSN: 1097458X     Source Type: Journal    
DOI: 10.1002/mrc.2570     Document Type: Article

References (223)

1. (a) R. Noyori, Chem. Soc. Rev. 1989, 18, 187
2. (b) R. Noyori, H. Takaya, Acc. Chem. Res. 1990, 23, 345
3. (c) W. S. Knowles, Angew. Chem. 2002, 114, 2097
4. J. G. de Vries, C. J. Elsevier (Eds), The Handbook of Homogeneous Hydrogenation, Wiley-VCH: Weinheim, 2007, pp3-70 deal with Rh, Ir, Ru, and Os catalysts; pp 745-1324 are devoted to asymmetric homogeneous Hydrogenation
5. (e) M. J. Krisch, Y. Sun (Eds). Acc. Chem. Res. 2007, 40, 1237; For a cationic (NHC)(pyridine)Ir complex as alkene hydrogenation catalyst, cf.
6. (f) H. M. Lee, T. Jiang, E. D. Stevens, S. P. Nolan, Organometallics 2001, 20, 1255;
7. For NHC-Rh/Ir catalysts for the transfer hydrogenation of ketones (g) H. Türkmen, T. Pape, F. E. Hahn, B. Çetinkaya, Organometallics 2008, 27, 571.
8. (a) R. H. Grubbs, S. Chang, Tetrahedron 1998, 54, 4413
9. (b) T. M. Trnka, R. H. Grubbs, Acc. Chem. Res. 2001, 34, 18
10. (c) S. J. Connon, S. Blechert, Angew. Chem. 2003, 115, 1944
11. (d) Angew. Chem., Int. Ed. 2003, 42, 1900
12. (d) Y. Chauvin, Angew. Chem. 2006, 118, 3825
13. (e) R. R. Schrock, Angew. Chem. 2006, 118, 3832
14. (f) R. H. Grubbs, Angew. Chem. 2006, 118, 3845
15. (g) R. H. Grubbs, R. R. Schrock, A. F̈urstner (Eds). Olefin Metathesis [Topical Issue], Adv. Synth. And Catal. 2007, 349, 1.
16. (a) E. Despagnet-Ayoub, T. Ritter, in N-Heterocyclic Carbenes in TransitionMetalCatalysis, vol.21, Topics inOrganometallicChemistry, (Ed.: F. Glorius), Springer Verlag: Berlin, 2007, p 193
17. (b) S. Beligny, S. Blechert, in N-Heterocyclic Carbenes in Synthesis (Ed.: S. P. Nolan), Wiley-VCH: Weinheim, 2006, p 1.
18. (a) T. Weskamp, W. C. Schattenmann, M. Spiegler, W. A. Herrmann, Angew. Chem. 1998, 110, 2631
19. (b) Angew. Chem., Int. Ed. 1998, 37, 2490
20. (b) M. Scholl, S. Ding, C.W. Lee, R. H. Grubbs, Org. Lett. 1999, 1, 953
21. (c) M. Scholl, T. M. Trnka, J. P. Morgan, R. H. Grubbs, Tetrahedron Lett. 1999, 40, 2247
22. (d) C.W. Bielawski, R. H. Grubbs, Angew. Chem. 2000, 112, 3025
23. Angew. Chem., Int. Ed. 2000, 39, 2903
24. (e) L. Delaude, A. Demonceau, A. F. Noels, Chem. Commun. 2001, 986
25. (f) T. M. Trnka, J. P. Morgan, M. S. Sanford, T. E. Wilhelm, M. Scholl, T.-L. Choi, S. Ding, M.W. Day, R. Grubbs, J. Am. Chem. Soc. 2003, 125, 2546
26. (g) R. H. Grubbs (Ed.), Handbook of Metathesis, Wiley-VCH: Weinheim, 2003; (
27. (h) V. Ćesar, S. Bellemin-Laponnaz, L. H. Gade, Chem. Soc. Rev. 2004, 33, 619.
28. (a) W. A. Herrmann, C. K̈ocher, Angew. Chem. 1997, 109, 2256
29. Angew. Chem., Int. Ed. Engl. 1997, 36, 2162
30. (b) A. J. Arduengo III, Acc. Chem. Res. 1999, 32, 913
31. (c) T. Weskamp, V. P.W. B̈ohm, W. A. Herrmann, J. Organomet. Chem. 2000, 600, 12
32. (d) W. A. Herrmann, Angew. Chem. 2002, 114, 1342
33. Angew. Chem., Int. Ed. 2002, 41, 1290
34. (e) C. M. Crudden, D. P. Allen, Coord. Chem. Rev. 2004, 248, 2247 (pp. 2260-2264 Ru, Rh, Ir complexes)
35. (f) N. M. Scott, S. P. Nolan, Eur. J. Inorg. Chem. 2005, 1815
36. (g) W. A. Herrmann, J. Scḧutz, G. D. Frey, E. Herdtweck, Organometallics 2006, 25, 2437 (Rh and Ir complexes)
37. (h) R. H. Crabtree (Ed.), Coord. Chem. Rev. 2007, 251, 595
38. (a) W. A. Herrmann, L. J. Gooßen, C. K̈ocher, G. R. J. Artus, Angew. Chem. 1996, 108, 2980
39. Angew. Chem., Int. Ed. Engl. 1996, 35, 2805
40. (b) S. Lee, J. F. Hartwig, J. Org. Chem. 2001, 66, 3402
41. (c) W. A. Herrmann, D. Baskakov, E. Herdtweck, S. D. Hoffmann, T. Bunlaksananusorn, F. Rampf, L. Rodefeld, Organometallics 2006, 25, 2449; For NHC-Pd and NHC-Ir complexes with planar-chiral [2,2]paracyclophanyl substituents cf.
42. (d) Y.Ma, C.Song, C.Ma, Z. Sun, Q. Chai,M. B. Andrus, Angew. Chem. 2003, 115, 6051
43. Angew. Chem., Int. Ed. 2003, 42, 5871
44. (e) T. Focken, G. Raabe, C. Bolm, Tetrahedron: Asymmetry 2004, 15, 1693
45. (a) H. Brunner, R. Oeschey, B. Nuber, Inorg. Chem. 1995, 34, 3349
46. (b) H. Brunner, R. Oeschey, B. Nuber, J. Chem. Soc., Dalton Trans. 1996, 1499
47. (c) H. Brunner, R. Oeschey, B. Nuber, Organometallics 1996, 15, 3616
48. (d) H. Brunner, A. K̈ollnberger, T. urgemeister, M. Zabel, Polyhedron 2000, 19, 1519
49. (e) H. Brunner, T. Zwack, Organometallics 2000, 19, 2423
50. (f) H. Brunner, Eur. J. Inorg. Chem. 2001, 905
51. (g) A. B̈ohm, H. Brunner, W. Beck, Z. Anorg. Allg. Chem. 2008, 634, 274
52. (h) H. Brunner, M. Muschiol, T. Tsuno, T. Takahashi, M. Zabel, Organometallics 2008, 27, 3514.
53. (a) P. Govindaswamy, D. Linder, J. Lacour, G. S̈ uss-Fink, B. Therrien, Chem. Commun. 2006, 4691
54. (b) P. Govindaswamy, D. Linder, J. Lacour, G. S̈ uss-Fink, B. Therrien, Dalton Trans. 2007, 4457.
55. P. Govindaswamy, G. Süss-Fink, B. Therrien, Organometallics 2007, 26, 915.
56. (a) B. Therrien, Eur. J. Inorg. Chem. 2009, 2445
57. (b) N. P. E. Barry, M. Austeri, J. Lacour, B. Therrien, Organometallics 2009, 28, 4894.
58. (a) F. V̈ogtle, Cyclophan-Chemie. Synthesen, Strukturen, Reaktionen, B. G. Teubner: Stuttgart, 1990
59. (b) H. Hopf, Classics in Hydrocarbon Chemistry: The Cyclophanes, Wiley-VCH: Weinheim, New York, Chichester, Brisbane, Singapore, Toronto, 2000, pp 337.
60. (a) M. Fujita, J. Yazaki, K. Ogura, J. Am. Chem. Soc. 1990, 112, 5645
61. (b) M. Fujita, J. Yazaki, K. Ogura, Chem. Lett. 1991, 1031
62. (c) M. Fujita, D. Oguro, M. Miyazawa, H. Oka, K. Yamaguchi, K. Ogura, Nature 1995, 378, 469 (with tpt triangles)
63. (d) M. Fujita, F. Ibukuro, K. Yamaguchi, K. Ogura, J. Am. Chem. Soc. 1995, 117, 4175
64. (e) M. Fujita, K. Ogura, Coord. Chem. Rev. 1996, 148, 249
65. (f) P. J. Stang, B. Olenyuk, Acc. Chem. Res. 1997, 30, 502
66. (g) G. F. Swiegers, T. J. Malefetse, Chem. Rev. 2000, 100, 3483
67. (h) B. J. Holliday, C. A. Mirkin, Angew. Chem. 2001, 113, 2076
68. Angew. Chem., Int. Ed. 2001, 40, 2022
69. (i) M. Fujita, K. Umemoto, M. Yoshizawa, N. Fujita, T. Kusukawa, K. Biradha, Chem. Commun. 2001, 509 (with tpt triangles).
70. (a) A. H. Velders, A. C.G. Hotze, J. G.Haasnoot, J. Reedijk, Inorg. Chem. 1999, 38, 2762; For arene-Ru complexes as candidates for anticancer therapy, cf.;
71. For arene-Ru complexes as candidates for anticancer therapy, cf. (b) Y. K. Yan, M. Melchart, A. Habtemariam, P. J. Sadler, Chem. Commun. 2005, 4764
72. (c) W. H. Ang, E. Daldini, C. Scolaro, R. Scopelliti, L. Juillerat-Jeannerat, P. J. Dyson, Inorg. Chem. 2006, 45, 9006.
73. Since there is no unanimity whether the ligand to transition metal coordinative bond is essentially a covalent bond or not, such complexes are assigned either to molecular or to supramolecular chemistry, and not infrequently to both. Cf., e.g. a B. J. Holliday, C. A. Mirkin, Angew. Chem. 2001, 113, 2076
74. Angew. Chem., Int. Ed. 2001, 40, 2022
75. (b) D. E. Janzen, K. N. Patel, D. G. VanDerveer, G. J. Grant, Chem. Commun. 2006, 3540
76. (c) S. Liu, B. C. Gibb, Chem. Commun. 2008, 3709.
77. K. Mislow, Introduction to Stereochemistry, W. A. Benjamin: Menlo Park, 1965, pp 78.
78. J.-M. Lehn, Pure Appl. Chem. 1978, 50, 871.
79. G. P. Schiemenz, H. Rast, Tetrahedron Lett. 1969, 2165.
80. (a) G. P. Schiemenz, Chemie-Ing.-Techn. 1972, 44, 442
81. (b) G. P. Schiemenz, J.Magn. Reson. 1972, 6, 291
82. (c) G. P. Schiemenz,H. Rast, Tetrahedron Lett. 1972, 1697
83. (d) G. P. Schiemenz, J. Organomet. Chem. 1973, 52, 349
84. (e) G. P. Schiemenz, Org. Magn. Reson. 1973, 5, 257
85. (f) G. P. Schiemenz, J. Mol. Struct. 1973, 16, 99
86. (g) G. P. Schiemenz, Tetrahedron 1973, 29, 741
87. (h) G. P. Schiemenz, H.-P. Hansen, Angew. Chem. 1973, 85, 404
88. Angew. Chem., Int. Ed. Engl. 1973, 12, 400
89. (i) G. P. Schiemenz, in Organic Sulphur Chemistry. Structure, Mechanism and Synthesis (Ed.: C. J.M. Stirling), Butterworths: London, Boston, 1975, p 320
90. (j) G. P. Schiemenz, M. Sommerfeld, Phosphorus Sulfur 1979, 6, 273
91. (k) G. P. Schiemenz, E. Papageorgiou, Phosphorus Sulfur 1982, 13, 41
92. (l) G.P. Schiemenz, R. Hinz, Phosphorus Sulfur 1983, 18, 237.
93. (a) G. P. Schiemenz, Angew. Chem. 1971, 83, 929
94. Angew. Chem., Int. Ed. Engl. 1971, 10, 855
95. (b) G. P. Schiemenz, P. Klemm, Org. Magn. Reson. 1974, 6, 276.
96. G. P. Schiemenz, J. Pistor, ACS Symposium Series 1981, 171, 567.
97. G. P. Schiemenz, J. Pistor, M. Wolf, Chem. Scripta 1981, 18, 67.
98. G. P. Schiemenz, J. Pistor, Chem. Scripta 1984, 23, 216.
99. M. R. Rosenthal, J. Chem. Educ. 1973, 50, 331
100. cf. S. H. Strauss, Chem. Rev. 1993, 93, 927.
101. G. Boche, Angew. Chem. 1992, 104, 742
102. Angew. Chem., Int. Ed. Engl. 1992, 31, 731.
103. D. Hellwinkel, Chem. Ber. 1966, 99, 3628, 3660.
104. (a) S. D. Bergman,R. Frantz,D. Gut,M. Kol, J. Lacour,Chem.Commun. 2006, 850
105. (b) J. Lacour, D. Linder, Chem. Rec. 2007 7, 275 and preceding papers.
106. Δ-BINPHAT (selected references)
107. (a) J. Lacour, A. Londez, C. Goujon-Ginglinger, V. Buss, G. Bernardinelli, Org. Lett. 2000, 2, 4185
108. (b) J. Lacour, L. Vial, C. Herse, Org. Lett. 2002, 4, 1351
109. (c) C. Pasquini, V. Desvergnes-Breuil, J. J. Jodry, A. Dalla Cort, J. Lacour, Tetrahedron Lett. 2002, 43, 423
110. (d) L. Pasquato, C. Herse, J. Lacour, Tetrahedron Lett. 2002, 43, 5517
111. (e) C. Herse, D. Bas, F. C. Krebs, T. B̈urgi, J. Weber, T. Wesolowski, B.W. Laursen, J. Lacour, Angew.Chem. 2003, 115, 3270
112. Angew.Chem.,Int.Ed. 2003, 42, 3162
113. (f) B. Laleu, G. Bernardinelli, R. Chauvin, J. Lacour, J. Org. Chem. 2006, 71, 7412.
114. K. Mislow, M. Raban, Topics Stereochem.1967, 1, 1.
115. K. A. Lyssenko, M. Yu. Antipin, D. Yu. Antonov, Chem. Phys. Chem. 2003, 4, 817.
116. W. Winter,V. Langjahr,H. Meier, J. Merkuschew, J. Juriew, Chem.Ber. 1984, 117, 2452.
117. G. Hughes, C. Wang, A. S. Batsanov, M. Fern, S. Frank, M. R. Bryce, I. F. Perepichka, A. P. Monkman, B. P. Lyons, Org. Biomol. Chem. 2003, 1, 3069.
118. M. S. Farag, Acta Crystallogr. 1954, 7, 117.
119. E.g. a J. J. Daly, J. Chem. Soc. 1964, 3799
120. (b) K. Mislow, D. Gust, P. Finocchiaro, R. J. Boetcher, Top. Curr. Chem. 1974, 47, 1
121. (c) J. A. S. Howell, M. G. Palin, P. C. Yates, P. McArdle, D. Cunningham, Z. Goldschmidt, H. E. Gottlieb, D. Hezroni-Langerman, J. Chem. Soc., Perkin Trans. 2 1992, 1769
122. (d) J. Polowin, S. C. Mackie, M. C. Baird, Organometallics 1992, 11, 3724
123. (e) S. E. Garner, A. G. Orpen, J. Chem. Soc., Dalton Trans. 1993, 533
124. (f) H. Brunner, R. Oeschey, B. Nuber, Angew. Chem. 1994, 106, 941
125. Angew. Chem., Int. Ed. Engl. 1994, 33, 866
126. (g) C. Palau, J. Phys. Chem. 1995, 99, 158
127. (h) J. A. S. Howell, N. Fey, J. D. Lovatt, P. C. Yates, P. McArdle, D. Cunningham, E. Sadeh, H. E. Gottlieb, Z. Goldschmidt, M. B. Hursthouse, M. E. Light, J. Chem. Soc., Dalton Trans. 1999, 3015.
128. (h) A. Pint́er, G. Haberhauser, I. Hyla-Kryspin, S. Grimme, Chem. Commun. 2007, 3711.
129. (a) J. F. Blount, P. Finocchiaro, D. Gust, K. Mislow, J. Am. Chem. Soc. 1973, 95, 7019
130. (b) K. Mislow, Acc. Chem. Res. 1976, 9, 26.
131. (a) M. A. Bennett, A. K. Smith, J. Chem. Soc., Dalton Trans. 1974, 233
132. (b) P. M. Maitlis, Chem. Soc. Rev. 1981, 10, 1
133. (c) M. A. Bennett, T.-N. Huang, T. W. Matheson, A. K. Smith, Inorg. Synth. 1982, 21, 74.
134. (a) S. Attar, J.H.Nelson, J. Fischer, A. de Cian, J.-P. Sutter,M. Pfeffer, Organometallics 1995, 14, 4559; Cf.
135. Cf b P. Pertici, E. Pitzalis, F. Marchetti, C. Rosini, P. Salvadori, M. A. Bennett, J. Organomet. Chem. 1994, 466, 221.
136. (a) J. A. Love,M. S. Sanford,M. W. Day, R. H. Grubbs,J.Am.Chem.Soc. 2003, 125, 10103; However, cases are known in which phosphines replace n6-cymene, albeit only at elevated temperatures or photochemically
137. (b) H. Katayama, F. Ozawa, Organometallics 1998, 17, 5190
138. E. Solari, S. Gauthier, R. Scopelliti, K. Severin, Organometallics 2009, 28, 4519.
139. A. Demonceau, A. W. Stumpf, E. Saive, A. F. Noels, Macromolecules 1997, 30, 3127.
140. Cf. R.H. Crabtree, J. Organomet. Chem. 2005, 690, 5451.
141. (a) M. S. Sanford, J. A. Love, R.H.Grubbs, Organometallics 2001, 20, 5314; Cf.
142. Cf. b M. A. Bennett, A. K. Smith, J. Chem. Soc., Dalton Trans. 1974, 233 ((1,3,5-Me3C6H3)RuCl2(pyridine) loses pyridine before melting at 296 °C)
143. (c) L. Ray, M. M. Shaikh, P. Ghosh, Dalton Trans. 2007, 4546 (pyridine as a throwaway ligand in NHC-Pd complexes)
144. (d) S. J. Dickson, S. C. G. Biagini, J. W. Steed, Chem. Commun. 2007, 4955.
145. M. A. Bennett, T.-N. Huang, T.W. Matheson, A. K. Smith, Inorg. Synth.1982, 21, 74 ([(n6-cymene)RuCl2]2, δ 4.60-4.72, not a "doublet of doublets, C6H4, J = 6 Hz", but two doublets for the H-2,6 and the H-3,5 protons)
146. (b) K. Mashima, S.-I. Kaneko, K. Tani, H. Kaneyoshi, A. Nakamura, J. Organomet. Chem. 1997, 545-546, 345
147. (c) H. Yan, G. S̈uss-Fink, A. Neels, H. Stoeckli-Evans, J. Chem. Soc., Dalton Trans. 1997, 4345
148. (d) L. Jafarpour, J. Huang, E. D. Stevens, S. P. Nolan, Organometallics 1999, 18, 3760 (compounds 7 and 8; some inconsistencies)
149. (e) D. Jan, L. Delaude, F. Simal, A. Demonceau, A. F. Noels, J. Organomet. Chem. 2000, 606, 55
150. 3 J = 6.9 Hz)
151. 3 J = ca. 6-7Hz)
152. (h) A. B. Chaplin, R. Scopelliti, P. J. Dyson, Eur. J. Inorg. Chem. 2005, 4762
153. (i) D. Zuccaccia, G. Bellachioma, G. Cardaci, G. Ciancaleoni, C. Zuccaccia, E. Clot, A. Macchioni, Organometallics 2007, 26, 3930
154. (j) C. A. Vock, C. Scolaro, A. D. Phillips, R. Scopelliti, G. Sava, P. J. Dyson, J.Med. Chem. 2006, 49, 5552
155. (k) C. A. Vock, R. Scopelliti, P. J. Dyson, Eur. J. Inorg. Chem. 2007, 3320
156. (l) W. H. Ang, E. Daldini, C. Scolaro, R. Scopelliti, L. Juillerat-Jeannerat, P. J. Dyson, Inorg. Chem. 2006, 45, 9006. (Ar-H: not dd, but 2d)
157. (m) C. A. Vock, W. H. Ang, C. Scolaro, A. D. Phillips, L. Lagopoulos, L. Juillerat-Jeanneret, G. Sava, R. Scopelliti, P. J. Dyson, J. Med. Chem. 2007, 50, 2166
158. (n) C. A. Vock, P. J. Dyson, Z. Anorg. Allg. Chem. 2007, 633, 640
159. (o) A. B. Chaplin, P. J. Dyson, Organometallics 2007, 26, 2447, 4357
160. (p) S. Bolãno, G. Ciancaleoni, J. Bravo, L. Gonsalvi, A. Macchioni, M. Peruzzini, Organometallics 2008, 27, 1649
161. 3 J coupling constants reported both for Harom. (4.8 Hz) and CHMe2 (5.5 Hz) of p-cymene)
162. (r) Y.- F. Han, W.-G. Jia, Y.-J. Lin, G.-X. Jin, Organometallics 2008, 27, 5002 (some inconsistencies, e.g. singlets for CHMe2 in compounds 4a-c, two "singlets" for compound 4d)
163. (s) A. Prades, M. Viciano, M. Sanaú, E. Peris, Organometallics 2008, 27, 4254
164. (t) J. Mattsson, P. Govindaswamy, J. Furrer, Y. Sei, K. Yamaguchi, G. S̈uss-Fink, B. Therrien, Organometallics 2008, 27, 4346
165. (u) J. Wolf, K. Thommes, O. Briel, R. Scopelliti, K. Severin, Organometallics 2008, 27, 4464
166. (v) M. Auzias, B. Therrien, G. Süss- Fink, P. Čtepnička, W. H. Ang, P. J. Dyson, Inorg. Chem. 2008, 47, 578
167. (w) P. Govindaswamy, J. Furrer, G. S̈ uss-Fink, B. Therrien, Z. Anorg. Allg. Chem. 2008, 634, 1349
168. (x) C. A. Vock, A. K. Renfrew, R. Scopelliti, L. Juillerat-Jeanneret, P. J. Dyson, Eur. J. Inorg. Chem. 2008, 1661
169. (y) O. Kaufhold, A. Flores-Figueroa, T. Pape, F. E. Hahn, Organometallics2009, 28, 896
170. (z) L. Delaude,X. Sauvage, A. Demonceau, J. Wouters, Organometallics 2009, 28, 4056
171. (aa) J. Martincová, R. Dostálová, L. Dost́ al, A. Ružička, R. Jambor, Organometallics 2009, 28, 4823
172. (ab) M. Yadav, A. K. Singh, B. Maiti, D. S. Pandey, Inorg. Chem. 2009, 48, 7593
173. (ac) C. Zhang, Y. Zhao, B.Li, H.Song, S.Xu, B.Wang, Dalton Trans. 2009, 5182 (with inconsistencies, e.g. J = 30.3 Hz in compound 6). Cf.
174. (ad) M. J. H. Russell, C. White, A. Yates, P. M. Maitlis, J. Chem. Soc., Dalton Trans. 1978, 857 (1H-NMR: unresolvedmat δ 6.83, butwell-resolved 13C-NMR spectrum).
175. 2; no data for arom. H given)
176. (b) S. K. Mandal,A. R. Chakravarty, J. Chem. Soc., Dalton Trans. 1992, 1627 (two diastereomers due to a chiral C atom in a ligand and a chiral Ru atom; in each four arom. H doublets mistaken for "two AB quartets in the range δ4.75-5.51" (J = 6-7 Hz)
177. (c) S. K. Mandal, A. R. Chakravarty, Inorg. Chem. 1993, 32, 3851 (one diastereomer of a Ru complex with a chiral C atom in a ligand and a chiral Ru atom, the four doublets of arom. H described as δ "5.77, 5.88 (q×2, 4H [J =]6 [Hz])"
178. (d) H. Brunner, R. Oeschey, B. Nuber, Inorg. Chem. 1995, 34, 3349 (a (n6-cymene)(γ -picoline)RuII complex with central chirality at Ru and at C in a ligand; one diastereomer: cymene arom. H: 2 AB systems; no non-equivalence of py-H-2,6 and py-H-3,5 (free rotation around the N-Ru bond)
179. (e) K.-J. Haack, S. Hashiguchi, A. Fujii, T. Ikariya, R. Noyori, Angew. Chem. 1997, 109, 297
180. Angew. Chem., Int. Ed. Engl. 1997, 36, 285
181. (f) D. Jan, L. Delaude, F. Simal, A. Demonceau, A. F. Noels, J. Organomet. Chem. 2000, 606, 55 ((n6-cymene)RuCl2(ER2R′ ), E = P, As, Sb. Note that for achiral complexes, either accidental isochrony has been observed, or a distinct δ value has been assigned to a multiplet integrating for 4H. The range of δ 5.49-5.53 for a phosphine complex with a chiral C atom in R' indicates a broader multiplet and thereby the anisochrony of all four protons)
182. (g) G. Ciancaleoni, G. Bellachioma, G. Cardaci, G. Ricci, R. Ruzziconi, D. Zuccaccia, A. Macchioni, J. Organomet. Chem. 2006, 691, 165 (a chiral Ru centre in addition to the planar chirality of a monosubstituted [2,2]-paracyclophane group in a bidentate ligand; data of one pure diastereomer)
183. (h) P. J. Bailey, D. Lorono-Gonzales, C. McCormack, F. Millican, S. Parsons, R. Pfeifer, P. P. Pinho, F. Rudolphi, A. Sanchez Perucha, Chem. Eur. J. 2006, 12, 5293
184. (i) P. J. Bailey, C. McCormack, S. Parsons, F. Rudolphi, A. Sanchez Perucha, P.Wood, Dalton Trans. 2007, 476
185. (j) G. Ciancaleoni, C. Zuccaccia, D. Zuccaccia, E. Clot, A. Macchioni, Organometallics 2009, 28, 960
186. (k) E. Solari, S. Gauthier, R. Scopelliti, K. Severin, Organometallics 2009, 28, 4519
187. (l) K. Kunz, M. Bolte, M.Wagner, H.-W. Lerner, Z. Anorg. Allg. Chem. 2009, 1580.
188. (a) D. L. Davies, J. Fawcett, R. Krafczyk, D. R. Russell, K. Singh, J. Chem. Soc., Dalton Trans. 1998, 2349
189. (b) L. Jafarpour, J. Huang, E. D. Stevens, S. P. Nolan, Organometallics 1999, 18, 3760 (compound 9)
190. (c) W. Henderson, B. K. Nicholson, A. G. Oliver, C. E. F. Rickard, J. Organomet. Chem. 2001, 625, 40
191. (d) L. Quebatte, E. Solari, R. Scopelliti, K. Severin, Organometallics 2005, 24, 1404 (anisochrony observed only for the arom. H's)
192. (e) A. B. Chaplin, C. Fellay, G. Laurenczy, P. J. Dyson, Organometallics 2007, 26, 586
193. (f) C. Scolaro, A. B. Chaplin, C. G. Hartinger, A. Bergamo, M. Cocchietto, B. K. Keppler, G. Sava, P. J.Dyson, Dalton Trans. 2007, 5065
194. (g) W. Henderson, T. D. Kilpin, B. K. Nicholson, Struct. Chem. 2008, 19, 199
195. (h) R. Schnecker, R. O. John, M. A. Jakupec, V. B. Arion, B. K. Keppler, Organometallics 2008, 27, 6587
196. (i) T. Kimura, H. Arita, K. Ishiwata, S. Kuwata, T. Ikariya, Dalton Trans. 2009, 2912
197. (j) D. Gnanamgari, E. L. O. Sauer, N. D. Schley, C. Butler, C. D. Incarvito, D. H. Crabtree, Organometallics 2009, 28, 321
198. (k) A. K. Renfrew, A. D. Phillips, A. E. Egger, C. G. Hartinger, S. S. Bosquain,A. A. Nazarov, B. K. Keppler, L. Gonsalvi,M. Peruzzini, P. J., Dyson, Organometallics 2009, 28, 1165
199. An exception (B. De Clercq, F. Lefebvre, F. Verpoort, New J. Chem. 2002, 26, 1201)
200. can be ascribed to kinetic instability of the three Ru-heteroatom bonds at the piano stool sites which are weaker than the n6-arene-Ru coordination. In a (n6-cymene)→Ru complex with formally chiral Ru(O2P) coordination and a notoriously weak O-ligand (acetone), H(arom) gives four broadened signals: A. B. Chaplin, P. J. Dyson, Organometallics 2007, 26, 4357.
201. (a) H. Brunner, Angew. Chem. 1999, 111, 1248
202. Angew. Chem., Int. Ed. 1999, 38, 1194
203. (b) V. Cadierno, J. Díez, J. García-Álvarez, J. Gimeno, Organometallics 2008, 27, 1809; For geminal enantiotopic protons becoming diastereotopic and hence anisochronous by Ruchirality cf.
204. (c) M. Hirano, T. Kuga, M. Kitamura, S. Kanaya, N. Komine, S. Komiya, Organometallics 2008, 27, 3635.
205. R. O. Hutchins, L. D. Kopp, E. L. Eliel, J.Am.Chem.Soc. 1968, 90, 7174.
206. E. J. Gabe, Y. Le Page, L. Prasad, G. R. Weisman, Acta Crystallogr. B 1982, 38, 2752
207. (b) E. J. Gabe, L. Prasad, G. R. Weisman, V. B. Johnson, Acta Crystallogr. C 1983, 39, 275
208. (c) M. Shoja, S. Saba, Acta Crystallogr. C 1993, 49, 354
209. (d) G. Royal, V. Dahaoui-Gindrey, S. Dahaoui, A. Tabard, R. Guilard, P. Pullumbi, C. Lecomte, Eur. J.Org. Chem. 1998, 1971
210. (e) T. Hokelek, N. Akduran, S. Bilge, Z. Kilic, Anal. Sci. 2001, 17, 465.
211. (a) J. Kroon,A. F. Peerdeman, J. M. Bijvoet,ActaCrystallogr.1965, 19, 293; A related case has recently been provided by a cryptand type S6As2 compound in which the arrangement of the three C15H14 chains connecting two S atoms imposes helical chirality in the crystal while the NMR spectra indicate no chirality because of rapid conformational changes
212. (b) M. A. Pitt, L. N. Zakharov, K. Vanka, W. H. Thompson, B. B. Laird, D. W. Johnson, Chem. Commun. 2008, 3936 (note that the compound is not a "supramolecular complex" but consists of conventional molecules because of the covalent character of the S-As bond).
213. G. A. Bootsma, J. C. Schoone, Acta Crystallogr.1967, 22, 522.
214. J. Kroon, J. A. Kanters, Acta Crystallogr. B 1973, 29, 1278.
215. (a) J. Kroon, J. A. Kanters, Acta Crystallogr. B 1972, 28, 714
216. (b) A. J. A. R. Blankensteyn, J. Kroon, Acta Crystallogr. C 1986, 42, 291
217. (c) P. F. W. Stouten, P. Verwers, B. P. van Eijck, J. Kroon, Acta Crystallogr. C 1988, 44, 1961.
218. A. J. De Vries, J. Kroon, Acta Crystallogr. C 1984, 40, 1542.
219. A. J. A. R. Blankensteyn, J. Kroon, Acta Crystallogr. C 1985, 41, 182.
220. J. Ascenso, V. M. S. Gil, Can. J. Chem. 1980, 58, 1376.
221. A. Ault, J. Chem. Educ. 2008, 85, 441.
222. J. Kroon, A. J. M. Duisenberg, A. F. Peerdeman, Acta Crystallogr. C 1984, 40, 645.
223. W. Moerman, M. Ouwerkerk, J. Kroon, Acta Crystallogr. C 1985, 41, 1205. Magn. Reson.