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2O, acetone) species. Two such compounds have been characterized crystallographically; see: (a) Crabtree, R. H.; Hlatky, G. G.; Parnell, C. P.; Segmüller, B. E.; Uriarte, R. J. Inorg. Chem. 1984, 23, 354-358. (b) Luo, X.-L.; Schulte, G. K.; Crabtree, R. H. Inorg. Chem. 1990, 29, 682-686.
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5
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2O, acetone) species. Two such compounds have been characterized crystallographically; see: (a) Crabtree, R. H.; Hlatky, G. G.; Parnell, C. P.; Segmüller, B. E.; Uriarte, R. J. Inorg. Chem. 1984, 23, 354-358. (b) Luo, X.-L.; Schulte, G. K.; Crabtree, R. H. Inorg. Chem. 1990, 29, 682-686.
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Recent publications by Werner et al. and Milstein et al. show that while neutral compounds of this type are dimeric, cationic complexes are stabilized by counterions or solvent molecules: (a) Canepa, G.; Brandt, C. D.; Werner, H. J. Am. Chem. Soc. 2002, 124, 9666-9667. (b) Gandelman, M.; Konstantinovski, L.; Rozenberg, H.; Milstein, D. Chem. Eur. J. 2003, 9, 2595-2602.
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Recent publications by Werner et al. and Milstein et al. show that while neutral compounds of this type are dimeric, cationic complexes are stabilized by counterions or solvent molecules: (a) Canepa, G.; Brandt, C. D.; Werner, H. J. Am. Chem. Soc. 2002, 124, 9666-9667. (b) Gandelman, M.; Konstantinovski, L.; Rozenberg, H.; Milstein, D. Chem. Eur. J. 2003, 9, 2595-2602.
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Crabtree, R.H.1
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σ-Donation through agostic interactions might be comparable in strength to σ-donation by acetone; see: Dorta, R.; Goikhman, R.; Milstein, D. Organometallics 2003, 22, 2806-2809.
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(a) Jazzar, R. F. R.; Macgregor, S. A.; Mahon, M. F.; Richards, S. P.; Whittlesey, M. K. J. Am. Chem. Soc. 2002, 124, 4944-4945.
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(b) Clement, N. D.; Cavell, K. J.; Jones, C.; Elsevier, C. J. Angew. Chem., Int. Ed. 2004, 43, 1277-1279.
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(c) Caddick, S.; Cloke, F. G. N.; Hitchcock, P. B.; Lewis, A. K. de K. Angew. Chem., Int. Ed. 2004, 43, 5824-5827.
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0142227781
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(a) Hillier, A. C.; Sommer, W. J.; Yong, B. S.; Peterson, J. L.; Cavallo, L.; Nolan, S. P. Organometallics 2003, 22, 4322-4326.
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(b) Dorta, R.; Stevens, E. D.; Hoff, C. D.; Nolan, S. P. J. Am. Chem. Soc. 2003, 125, 10490-10491.
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(c) Dorta, R.; Stevens, E. D.; Scott, N. M.; Costabile, C.; Cavallo, L.; Hoff, C. D.; Nolan, S. P. J. Am. Chem. Soc. 2005, 127, 2485-2495.
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28
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0000393279
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Whereas such cyclometalation processes are well-documented and rather common for bulky phosphine and nitrogen-donor ligands, they have been rarely observed in NHCs. An example of intramolecular C-H activation of an NHC on Rh (using the less bulky and less basic IMes ligand) has appeared: Huang, J.; Stevens, E. D.; Nolan, S. P. Organometallics 2000, 19, 1194-1197.
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Huang, J.1
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Dorta, R.; Stevens, E. D.; Nolan, S. P. J. Am. Chem. Soc. 2004, 126, 5054-5055.
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Dorta, R.1
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30
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2342529665
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A discussion on nonclassical vs classical agostic interactions can be found in the following reference: Baratta, W.; Mealli, C.; Hertweck, E.; Ienco, A.; Mason, S. A.; Rigo, P. J. Am. Chem. Soc. 2004, 126, 5549-5562.
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Baratta, W.1
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Rigo, P.6
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31
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1642454930
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Similarly fluctional behavior has recently been observed in a Ru-NHC complex: see: Abdur-Rashid, K.; Fedorkiw, T.; Lough, A. J.; Morris, R. H. Organometallics 2004, 23, 86-94.
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Abdur-Rashid, K.1
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34
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37049107497
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(c) Empsall, H. D.; Hyde, E. M.; Mentzer, E.; Shaw, B. L. J. Chem. Soc., Dalton Trans. 1977, 2285-2291.
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Empsall, H.D.1
Hyde, E.M.2
Mentzer, E.3
Shaw, B.L.4
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35
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33847797644
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-
The value found in 2 is similar to values for hydrides trans to O-bound ligands; see: (a) Schrock, R. R.; Osborn, J. A. J. Am. Chem. Soc. 1976, 98, 8, 2134-2142. (b) Rybtchinski, B.; Konstantinovsky, L.; Shimon, L. J. W.; Vigalok, A.; Milstein, D. Chem. Eur. J. 2000, 6, 3287-3292.
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Schrock, R.R.1
Osborn, J.A.2
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36
-
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0034282446
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The value found in 2 is similar to values for hydrides trans to O-bound ligands; see: (a) Schrock, R. R.; Osborn, J. A. J. Am. Chem. Soc. 1976, 98, 8, 2134-2142. (b) Rybtchinski, B.; Konstantinovsky, L.; Shimon, L. J. W.; Vigalok, A.; Milstein, D. Chem. Eur. J. 2000, 6, 3287-3292.
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Rybtchinski, B.1
Konstantinovsky, L.2
Shimon, L.J.W.3
Vigalok, A.4
Milstein, D.5
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37
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0009235705
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-
These distances might indicate a very weak agostic interaction; for comparison, see: Neve, F.; Ghedini, M.; Crispini, A. Organometatlics 1992, 11, 3324-3327.
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Neve, F.1
Ghedini, M.2
Crispini, A.3
-
38
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-
14944377876
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note
-
Complex 2 can be isolated on a preparative scale by decreasing the reaction time in benzene to 1 h, but contamination by already formed 4 is usually observed.
-
-
-
-
39
-
-
14944347800
-
-
note
-
13C NMR of 2 in benzene.
-
-
-
-
40
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14944345092
-
-
note
-
Dilution is important for the outcome of this reaction. When the reaction is carried out in a more concentrated pentane slurry/solution, the yellow precipitate contains various amounts of 2 (up to 30%).
-
-
-
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41
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37049136806
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-
See ref 9 and the following references: (a) Masters, C. J.; Shaw, B. L.; Stainbank, R. E. J. Chem. Soc., Chem. Commun. 1971, 209. (b) Moulton, C. J.; Shaw, B. L. J. Chem. Soc., Dalton Trans. 1976, 1020-1024. (c) Kanzelberger, M.; Singh, B.; Czerw, M.; Krogh-Jesperson, K.; Goldman, A. S. J. Am. Chem. Soc. 2000, 122, 11017-11018. (d) Ben-Ari, E.; Gandelman M.; Rozenberg, H.; Shimon, L. J. W.; Milstein, D. J. Am. Chem. Soc. 2003, 125, 4716-4717.
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(1971)
J. Chem. Soc., Chem. Commun.
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Masters, C.J.1
Shaw, B.L.2
Stainbank, R.E.3
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42
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37049103692
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-
See ref 9 and the following references: (a) Masters, C. J.; Shaw, B. L.; Stainbank, R. E. J. Chem. Soc., Chem. Commun. 1971, 209. (b) Moulton, C. J.; Shaw, B. L. J. Chem. Soc., Dalton Trans. 1976, 1020-1024. (c) Kanzelberger, M.; Singh, B.; Czerw, M.; Krogh-Jesperson, K.; Goldman, A. S. J. Am. Chem. Soc. 2000, 122, 11017-11018. (d) Ben-Ari, E.; Gandelman M.; Rozenberg, H.; Shimon, L. J. W.; Milstein, D. J. Am. Chem. Soc. 2003, 125, 4716-4717.
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(1976)
J. Chem. Soc., Dalton Trans.
, pp. 1020-1024
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Moulton, C.J.1
Shaw, B.L.2
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43
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0034623550
-
-
See ref 9 and the following references: (a) Masters, C. J.; Shaw, B. L.; Stainbank, R. E. J. Chem. Soc., Chem. Commun. 1971, 209. (b) Moulton, C. J.; Shaw, B. L. J. Chem. Soc., Dalton Trans. 1976, 1020-1024. (c) Kanzelberger, M.; Singh, B.; Czerw, M.; Krogh-Jesperson, K.; Goldman, A. S. J. Am. Chem. Soc. 2000, 122, 11017-11018. (d) Ben-Ari, E.; Gandelman M.; Rozenberg, H.; Shimon, L. J. W.; Milstein, D. J. Am. Chem. Soc. 2003, 125, 4716-4717.
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Kanzelberger, M.1
Singh, B.2
Czerw, M.3
Krogh-Jesperson, K.4
Goldman, A.S.5
-
44
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0037462117
-
-
See ref 9 and the following references: (a) Masters, C. J.; Shaw, B. L.; Stainbank, R. E. J. Chem. Soc., Chem. Commun. 1971, 209. (b) Moulton, C. J.; Shaw, B. L. J. Chem. Soc., Dalton Trans. 1976, 1020-1024. (c) Kanzelberger, M.; Singh, B.; Czerw, M.; Krogh-Jesperson, K.; Goldman, A. S. J. Am. Chem. Soc. 2000, 122, 11017-11018. (d) Ben-Ari, E.; Gandelman M.; Rozenberg, H.; Shimon, L. J. W.; Milstein, D. J. Am. Chem. Soc. 2003, 125, 4716-4717.
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Ben-Ari, E.1
Gandelman, M.2
Rozenberg, H.3
Shimon, L.J.W.4
Milstein, D.5
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45
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-
0000713467
-
-
(a) Crabtree, R. H.; Mellea, M. F.; Mihelcic, J. M.; Quirk, J. M. J. Am. Chem. Soc. 1982, 104, 107-113.
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Crabtree, R.H.1
Mellea, M.F.2
Mihelcic, J.M.3
Quirk, J.M.4
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46
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18244385292
-
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(b) Crabtree, R. H.; Demou, P. C.; Eden, D.; Mihelcic, J. M.; Parnell, C. A.; Quirk, J. M.; Morris, G. E. J. Am. Chem. Soc. 1982, 104, 6994-7001.
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Crabtree, R.H.1
Demou, P.C.2
Eden, D.3
Mihelcic, J.M.4
Parnell, C.A.5
Quirk, J.M.6
Morris, G.E.7
-
47
-
-
14944371552
-
-
note
-
8) show that the spectrum of 5 remains virtually unchanged in the range 297-233 K.
-
-
-
-
48
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0037664295
-
-
We are aware of one such example, involving double cyclometalation on an Ir-PCP system; see: Mohammad, H. A. Y.; Grimm, J. C.; Eichele, K.; Mack, H -G.; Speiser, B.; Novak, F.; Quintanilla, M. G.; Kaska, W. C.; Mayer, H. A. Organometallics 2002, 21, 5775-5784
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Mohammad, H.A.Y.1
Grimm, J.C.2
Eichele, K.3
Mack, H.G.4
Speiser, B.5
Novak, F.6
Quintanilla, M.G.7
Kaska, W.C.8
Mayer, H.A.9
-
49
-
-
0000578501
-
-
and references therein
-
Activation of aryl C-H bonds by Rh(III) has been proposed in the catalytic transfer dehydrocoupling of arenes and silanes: Ezbiansky, K.; Djurovich, P. I.; LaForest, M.; Sinning, D. J.; Zayes, R.; Berry, D. H. Organometallics 1998, 17, 1455-1457 and references therein.
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Ezbiansky, K.1
Djurovich, P.I.2
LaForest, M.3
Sinning, D.J.4
Zayes, R.5
Berry, D.H.6
-
50
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0003369765
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-
For an example of an agostic Ir complex showing reversible metalation, see: Albeniz, A. C.; Schulte, G.; Crabtree, R. H. Organometallics 1992, 11, 242-249.
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(1992)
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Albeniz, A.C.1
Schulte, G.2
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51
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0000670416
-
-
Related examples of proton-hydride interactions involve close contacts between iridium(III) hydrides and a hydrogen atom coordinated to an electronegative heteroatom (O, N). Proton transfer from these acidic hydrogens to Ir-H and formation of iridium dihydrogen complexes have been observed; see: (a) Lough, A. J.; Park, S.; Ramachandran, R.; Morris, R. H. J. Am. Chem. Soc. 1994, 116, 8356-8357. (b) Lee, J. C. Jr.; Peris, E.; Rheingold, A. L.; Crabtree, R. H. J. Am. Chem. Soc. 1994, 116, 11014-11019. For a review on proton-hydride interactions, see: (c) Custelcean, R.; Jackson, J. E. Chem. Rev. 2001, 101, 1963-1980.
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Lough, A.J.1
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Ramachandran, R.3
Morris, R.H.4
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52
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0141640144
-
-
Related examples of proton-hydride interactions involve close contacts between iridium(III) hydrides and a hydrogen atom coordinated to an electronegative heteroatom (O, N). Proton transfer from these acidic hydrogens to Ir-H and formation of iridium dihydrogen complexes have been observed; see: (a) Lough, A. J.; Park, S.; Ramachandran, R.; Morris, R. H. J. Am. Chem. Soc. 1994, 116, 8356-8357. (b) Lee, J. C. Jr.; Peris, E.; Rheingold, A. L.; Crabtree, R. H. J. Am. Chem. Soc. 1994, 116, 11014-11019. For a review on proton-hydride interactions, see: (c) Custelcean, R.; Jackson, J. E. Chem. Rev. 2001, 101, 1963-1980.
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14944368409
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note
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Several X-ray structures shown here appear as mirror images of each other. This is due to the fact that they are chiral at the metal center and that an inversion center is imposed upon refinement of their structures.
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55
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14944377219
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note
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In the rhodium case, we observe decomposition to several unidentified products.
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14944383368
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note
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These do not give solvent-ligand adducts when dissolved in potentially coordinating solvents such as dichloromethane, THF, or acetone.
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14944381375
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note
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NHCs are better donor ligands than alkylphosphines; see ref 13.
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14944342359
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note
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The MO numbering follows the ADF output.
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14944360315
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note
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Evaporation and analysis of the mother liquor show formation of 2 (in addition to free ligand and traces of 1).
-
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-
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67
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14944359831
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note
-
Leaving the solution at room temperature for 3 days and subsequent workup result in a mixture of 2 (major) and 4 (minor).
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