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Chemistry

Methyl Complexes of the Transition Metals

Profile image of Riccardo PelosoRiccardo Peloso

2016, Chemistry (Weinheim an der Bergstrasse, Germany)

https://doi.org/10.1002/CHEM.201504483
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28 pages

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Abstract

Organometallic chemistry can be considered as a wide area of knowledge that combines concepts of classic organic chemistry, that is, based essentially on carbon, with molecular inorganic chemistry, especially with coordination compounds. Transition-metal methyl complexes probably represent the simplest and most fundamental way to view how these two major areas of chemistry combine and merge into novel species with intriguing features in terms of reactivity, structure, and bonding. Citing more than 500 bibliographic references, this review aims to offer a concise view of recent advances in the field of transition-metal complexes containing M-CH3 fragments. Taking into account the impressive amount of data that are continuously provided by organometallic chemists in this area, this review is mainly focused on results of the last five years. After a panoramic overview on M-CH3 compounds of Groups 3 to 11, which includes the most recent landmark findings in this area, two further sectio...

FAQs

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What explains the unique reactivity of transition metal methyl complexes?add

The paper reveals that the slender steric properties of methyl groups allow distinctive reactivity profiles, enabling elementary reactions essential for both academic and industrial transformations.

How do bridging methyl ligands influence metal-metal bonding?add

Research findings indicate that bridging methyl groups can act as three-center two-electron bonds, modifying metal-metal bonding interactions and creating agostic effects, particularly in polymetallic complexes.

What synthetic methods are preferred for generating TM-CH3 bonds?add

The study shows that common methods include metathesis with organometallic reagents and oxidative addition, with over 200 new methyl complexes reported annually.

When did the first hexamethyl transition metal compound emerge?add

WMe6, the first hexamethyl complex, was synthesized in the 1970s, initiating extensive research into transition metal methyl complexes.

Why are methyl complexes considered crucial in olefin polymerization?add

Recent studies emphasize their essential role as catalysts in Ziegler-Natta polymerization, due to their unique electronic structures and reactivity patterns.

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References (458)

  1. M. Bochmann, Organometallics and Catalysis, Oxford University Press, Oxford, UK, 2015.
  2. R. H. Crabtree, The Organometallic Chemistry of the Transition Metals, 6th ed., John Wiley & Sons, Inc, Hoboken, 2014.
  3. J. F. Hartwig, Organotransition Metal Chemistry: From Bonding to Catalysis, University Science Books, Casebound, 2010.
  4. C. Elschenbroich, Organometallics, 3rd ed., Wiley-VCH, Weinheim, 2006.
  5. Comprenhensive Organometallic Chemistry III, Vol. 1 (Ed.: K. Meyer), 3 (Ed.: C. E. Housecroft), 9 (Ed.: P. Knochel), 10 (Ed.: I. Ojima) and 11 (Ed. T. Hiyama) (Eds.: R. H. Crabtree, D. M. P. Mingos), Elsevier, Ltd., 2007.
  6. M. Schlosser, Organometallics in Synthesis, A Manual, John Wiley & Sons, Ltd., Chinchester, 2002.
  7. G. Wilkinson, Chimia 1973, 27, 3.
  8. A. J. Shortland, G. Wilkinson, J. Chem. Soc., Dalton Transactions 1973, 872; for early examples of hexamethyl anionic complexes see: b)
  9. R. S. Hay-Motherwell, G. Wilkinson, B. Hussain, M. B. Hursthousem J. Chem. Soc., Chem. Commun. 1989, 1436.; c) E. Kurras, J. Otto, J. Organomet. Chem. 1974, 65, 215;
  10. H. Schumann, J. Pickardt, N. Bruncks, Angew. Chem. Int. Ed. 1981, 20, 120;
  11. R. J. Morris, G. S. Girolami, J. Am. Chem. Soc. 1988, 110, 6245;
  12. P. M. Morse and G. S. Girolami, J. Am. Chem. SOC. 1989, 111, 4114;
  13. G. W. Rice, R. S. Tobias, J. Am. Chem. Soc. 1977, 99, 2141;
  14. C. S. Creaser, J. A. Creighton, J. Organomet. Chem. 1978, 157, 243.
  15. J. C. Green, M. L. H. Green, G. Parkin, Chem. Commun. 2012, 48, 11481.
  16. N. Curado, M. Carrasco, E. Álvarez, C. Maya, R. Peloso, A. Rodríguez, J. López-Serrano, E. Carmona, J. Am. Chem. Soc. 2015, 137, 12378.
  17. R. R. Schrock, J. Am. Chem. Soc. 1975, 97, 6577.
  18. W. H. Bernskoetter, C. K. Schauer, K. I. Goldberg, M. Brookhart, Science 2009, 326, 553.
  19. F. Allen, Acta Crystallographica Section B 2002, 58, 380.
  20. P. J. Davidson, M. F. Lappert, R. Pearce, Chemical Reviews 1976, 76, 219.
  21. Schrock, R. R.; Parshall, G. W. Chemical Reviews 1976, 76, 243.
  22. C.C.H.Atienza, C.Milsmann, E.Lobkovsky, P.J.Chirik, Angew. Chem. Int. Ed. 2011, 50, 8143.
  23. B. Zhu, X. Hao, Y. Chen, Organometallics 2014, 33, 240.
  24. L. J. Hounjet, R. McDonald, M. J. Ferguson, M. Cowie, Inorg. Chem. 2011, 50, 5361.
  25. M. Montag, I. Efremenko, Y. Diskin-Posner, Y. Ben-David, J. M. L. Martin, D. Milstein, Organometallics 2012, 31,505.
  26. T. Tanabe, M. E. Evans, W. W. Brennessel, W. D. Jones, Organometallics 2011, 30, 834.
  27. J. Campos, R. Peloso, M. Brookhart, E. Carmona, Organometallics 2013, 32, 3423.
  28. K. D. Wells, R. McDonald, M. J. Ferguson, M. Cowie, Organometallics 2011, 30, 2654.
  29. Schumann, J. A. Meese-Marktscheffel, L. Esser, Chemical Reviews 1995, 95, 865.
  30. M. Zimmermann, R. Anwander, Chem. Rev. 2010, 110, 6194.
  31. M. U. Kramer, D. Robert, S. Arndt, P. M. Zeimentz, T. P. Spaniol, A. Yahia, L. Maron, O. Eisenstein, J. Okuda, Inorg. Chem. 2008, 47, 9265.
  32. P. M. Zeimentz, S. Arndt, B. R. Elvidge, J. Okuda, Chem. Rev. 2006, 106, 2404-2433..
  33. L. N. Jende, C. Maichle-Mössmer, R. Anwander, Chem. Eur. J. 2013, 19, 16321.
  34. J. Hong, L. Zhang, X. Yu, M. Li, Z. Zhang, P. Zheng, M. Nishiura, Z. Hou, X. Zhou, Chem. Eur. J. 2011, 17, 2130.
  35. J. Zhou, J. Chu, Y. Zhang, G. Yang, X. Leng, Y. Chen, Angew. Chem. Int. Ed. 2013, 52, 4243-4246.
  36. A. Nieland, A. Mix, B. Neumann, H.-G. Stammler, N. W. Mitzel, Dalton Trans. 2010, 39, 6753.
  37. D. Bojer, A. Venugopal, A. Mix, B. Neumann, H.-G. Stammler, N. W. Mitzel, Chem. Eur. J. 2011, 17, 6248.
  38. G. Occhipinti, C. Meermann, H. M. Dietrich, R. Litlabø, F. Auras, K. W. Törnroos, C. Maichle-Mössmer, V. R. Jensen, R. Anwander, J. Am. Chem. Soc. 2011, 133, 6323.
  39. a) Monographic volume, Coord. Chem. Rev. 2006, 250, 1;
  40. M. Bochmann, Organometallics 2010, 29, 4711.
  41. L. Resconi, J. C. Chadwick, L. Cavallo, in Comprehensive Organometallic Chemistry III (Eds.: R. H. Crabtree, D. M. P. Mingos), Elsevier, Oxford, 2007, pp. 1005.
  42. T. Fujita, H. Makio, in Comprehensive Organometallic Chemistry III (Ed.: D. M. P. M. H. Crabtree), Elsevier, Oxford, 2007, pp. 691.
  43. E. G. Ijpeij, B. Coussens, M. A. Zuideveld, G. H. J. van Doremaele, P. Mountford, M. Lutz, A. L. Spek, Chem. Commun. 2010, 46, 3339.
  44. P. D. Bolton, E. Clot, A. R. Cowley, P. Mountford, J. Am. Chem. Soc. 2006, 128, 15005.
  45. G. Theurkauff, A. Bondon, V. Dorcet, J.-F. Carpentier, E. Kirillov, Angew. Chem. Int. Ed. 2015, 54, 6343.
  46. D. Shoken, M. Sharma, M. Botoshansky, M. Tamm, M. S. Eisen, J. Am. Chem. Soc. 2013, 135, 12592.
  47. A. Sattler, J. A. Labinger, J. E. Bercaw, Organometallics 2013, 32, 6899.
  48. A. Sattler, D. G. VanderVelde, J. A. Labinger, J. E. Bercaw, J. Am. Chem. Soc. 2014, 136, 10790.
  49. R. C. Neu, E. Otten, A. Lough, D. W. Stephan, Chem. Sci. 2011, 2, 170.
  50. A. Mukherjee, S. Nembenna, T. K. Sen, S. P. Sarish, P. K. Ghorai, H. Ott, D. Stalke, S. K. Mandal, H. W. Roesky, Angew. Chem. Int. Ed. 2011, 50, 3968.
  51. C. Lorber, in Comprehensive Organometallic Chemistry III (Eds.: R. H. Crabtree, D. M. P. Mingos), Elsevier, Oxford, 2007, pp. 1.
  52. A. Jabri, I. Korobkov, S. Gambarotta, R. Duchateau, Angew. Chem. Int. Ed. 2007, 46, 6119.
  53. Y. Onishi, S. Katao, M. Fujiki, K. Nomura, Organometallics 2008, 27, 2590;
  54. K. Mashima, S. Fujikawa, Y. Tanaka, H. Urata, T.i Oshiki, E. Tanaka, A. Nakamura, Organometallics 1995, 14, 2633.
  55. N. C. Tomson, J. Arnold, R. G. Bergman, Dalton Transactions 2011, 40, 7718.
  56. A. Sattler, S. Ruccolo, G. Parkin, Dalton Transactions 2011, 40, 7777.
  57. Y. Chen, E. Callens, E. Abou-Hamad, N. Merle, A. J. P. White, M. Taoufik, C. Copéret, E. Le Roux, J.-M. Basset, Angew. Chem. Int. Ed. 2012, 51, 11886.
  58. A. Sattler, G. Parkin, J. Am. Chem. Soc. 2012, 134, 2355.
  59. P. Garcia, Y. Y. Lau, M. R. Perry, L. L. Schafer, Angew. Chem. Int. Ed. 2013, 52, 9144-.
  60. V. Pfennig, K. Seppelt, Science 1996, 271, 626.
  61. B. Roessler, K. Seppelt, Angew. Chem. Int. Ed. 2000, 39, 1259.
  62. S. Kleinhenz, V. Pfennig, K. Seppelt, Chem. Eur. J. 1998, 4, 1687.
  63. V. Pfennig, K. Seppelt, N. Robertson, Angew. Chem. Int. Ed. 1997, 36, 1350.
  64. M. J. Carney, K. M. Smith, in Reference Module in Chemistry, Molecular Sciences and Chemical Engineering, Elsevier, 2013.
  65. T. Agapie, J. A. Labinger, J. E. Bercaw, J. Am. Chem. Soc. 2007, 129, 14281.
  66. I. Vidyaratne, G. B. Nikiforov, S. I. Gorelsky, S. Gambarotta, R. Duchateau, I. Korobkov, Angew. Chem. Int. Ed. 2009, 48, 6552.
  67. K. Albahily, Y. Shaikh, Z. Ahmed, I. Korobkov, S. Gambarotta, R. Duchateau, Organometallics 2011, 30, 4159.
  68. S. Licciulli, I. Thapa, K. Albahily, I. Korobkov, S. Gambarotta, R. Duchateau, R. Chevalier, K. Schuhen, Angew. Chem. Int. Ed. 2010, 49, 9225.
  69. K. A. Kreisel, G. P. A. Yap, K. H. Theopold, Eur. J. Inorg. Chem. 2012, 2012, 520.
  70. W. R. H. Wright, A. S. Batsanov, A. M. Messinis, J. A. K. Howard, R. P. Tooze, M. J. Hanton, P. W. Dyer, Dalton Trans. 2012, 41, 5502.
  71. W. R. H. Wright, A. S. Batsanov, J. A. K. Howard, R. P. Tooze, M. J. Hanton, P. W. Dyer, Dalton Trans. 2010, 39, 7038.
  72. T. Nguyen, A. D. Sutton, M. Brynda, J. C. Fettinger, G. J. Long, P. P. Power, Science 2005, 310, 844.
  73. A. Noor, R. Kempe, Inorg. Chim. Acta 2015, 424, 75.
  74. A. Noor, S. Schwarz, R. Kempe, Organometallics 2015, 34, 2122.
  75. R. Campbell, L. M. Carrella, W. Clegg, R. E. Mulvey, E. Rentschler, S. D. Robertson, L. Russo, Inorg. Chem. 2011, 50, 4656.
  76. J. Krausse, G. Marx, G. Schödl, J. Organomet. Chem. 1970, 21, 159.
  77. S. Hao, J.-I. Song, P. Berno, S. Gambarotta, Organometallics 1994, 13, 1326.
  78. J.-G. Ma, Y. Aksu, L. J. Gregoriades, J. Sauer, M. Driess, Dalton Trans. 2010, 39, 103-106.
  79. B. Sheridan, in Comprehensive Organometallic Chemistry III (Ed.: D. M. P. M. H. Crabtree), Elsevier, Oxford, 2007, pp. 815.
  80. M. A. Stewart, C. E. Moore, T. B. Ditri, L. A. Labios, A. L. Rheingold, J. S. Figueroa, Chem. Commun. 2011, 47, 406.
  81. W. A. Herrmann, R. Alberto, P. Kiprof, F. Baumgärtner, Angew. Chem. Int. Ed. 1990, 29, 189.
  82. C. C. Romão, B. Royo, in Comprehensive Organometallic Chemistry III (Eds.: R. H. Crabtree, D. M. P. Mingos), Elsevier, Oxford, 2007, pp. 855.
  83. S. A. Hauser, V. Korinth, E. Herdtweck, M. Cokoja, W. A. Herrmann, F. E. Kühn, Eur. J. Inorg. Chem. 2010, 2010, 4083.
  84. S. Liu, A. Senocak, J. L. Smeltz, L. Yang, B. Wegenhart, J. Yi, H. I. Kenttämaa, E. A. Ison, M. M. Abu-Omar, Organometallics 2013, 32, 3210.
  85. Y. Lee, N. P. Mankad, J. C. Peters, Nature Chem. 2010, 2, 558.
  86. A. M. Tondreau, C. Milsmann, A. D. Patrick, H. M. Hoyt, E. Lobkovsky, K. Wieghardt, P. J. Chirik, J. Am. Chem. Soc. 2010, 132, 15046.
  87. M. W. Bouwkamp, S. C. Bart, E. J. Hawrelak, R. J. Trovitch, E. Lobkovsky, P. J. Chirik, Chem. Commun. 2005, 3406.
  88. F. A. Jové, C. Pariya, M. Scoblete, G. P. A. Yap, K. H. Theopold, Chem. Eur. J. 2011, 17, 1310.
  89. J. L. Kisko, T. Hascall, G. Parkin, J. Am. Chem. Soc. 1998, 120, 10561.
  90. T. Hashimoto, S. Urban, R. Hoshino, Y. Ohki, K. Tatsumi, F. Glorius, Organometallics 2012, 31, 4474.
  91. J. A. Przyojski, H. D. Arman, Z. J. Tonzetich, Organometallics 2013, 32, 723.
  92. N. Kleigrewe, W. Steffen, T. Blömker, G. Kehr, R. Fröhlich, B. Wibbeling, G. Erker, J.-C. Wasilke, G. Wu, G. C. Bazan, J. Am. Chem. Soc. 2005, 127, 13955.
  93. S. Monfette, Z. R. Turner, S. P. Semproni, P. J. Chirik, J. Am. Chem. Soc. 2012, 134, 4561.
  94. J. V. Obligacion, P. J. Chirik, J. Am. Chem. Soc. 2013, 135, 19107.
  95. R. P. Yu, J. M. Darmon, C. Milsmann, G. W. Margulieux, S. C. E. Stieber, S. DeBeer, P. J. Chirik, J. Am. Chem. Soc. 2013, 135, 13168.
  96. E. Khaskin, Y. Diskin-Posner, L. Weiner, G. Leitus, D. Milstein, Chem. Commun. 2013, 49, 2771.
  97. A. Steffen, R. M. Ward, M. G. Tay, R. M. Edkins, F. Seeler, M. van Leeuwen, L. O. Palsson, A. Beeby, A. S. Batsanov, J. A. K. Howard, T. B. Marder, Chem. Eur. J. 2014, 20, 3652;
  98. W.J.Tenn III, B.L.Conley, S.M.Bischof, R.A.Periana, J. Organomet. Chem. 2011, 696, 551;
  99. J. R. Webb, T. M. Figg, B. M. Otten, T. R. Cundari, T. B. Gunnoe, M.Sabat, Eur. J. Inorg. Chem. 2013, 4515;
  100. S. A. Burgess, T. Bolano, T. B. Gunnoe, M. Sabat, W. H. Myers, Eur. J. Inorg. Chem. 2015, 1041;
  101. W.-M. Cheung, W.-H. Chiu, H. H. Y. Sung, I. D. Williams, W.-H. Leung, Eur. J. Inorg. Chem. 2014, 2961;
  102. L. Zamostna, S. Sander, T. Braun, R. Laubenstein, B. Braun, R. Herrmann, P. Kläring, Dalton Trans. 2015, 44, 9450.
  103. Y. Jiao, J. Morris, W. W. Brennessel, W. D. Jones, J. Am. Chem. Soc. 2013, 135, 16198;
  104. Y. Jiao, W. W. Brennessel, W. D. Jones, Chem. Sci. 2014, 5, 804;
  105. S. Wanniarachchi, B. J. Liddle, S. V. Lindeman, J. R. Gardinier, J. Organomet. Chem. 2011, 696, 3623;
  106. S. Wanniarachchi, J. S. Hewage, S. V. Lindeman, J. R. Gardinier, Organometallics 2013, 32, 2885;
  107. M. Montag, I. Efremenko, G. Leitus, Y. Ben-David, J. M. L. Martin, D. Milstein, Organometallics 2013, 32, 7163.
  108. J. J. Adams, N. Arulsamy, D. M. Roddick, Organometallics 2011, 30, 697;
  109. S. Kundu, J. Choi, D. Y. Wang, Y. Choliy, T. J. Emge, K. Krogh- Jespersen, A. S. Goldman, J. Am. Chem. Soc. 2013, 135, 5127.
  110. M. D.Walter, P. S. White, C. K. Schauer, M. Brookhart, New J. Chem. 2011, 35, 2884;
  111. J. Campos, S. Kundu, D. R. Pahls, M. Brookhart, E. Carmona, T. R. Cundari, J. Am. Chem. Soc. 2013, 135, 1217;
  112. J. G. Melnick, A. T. Radosevich, D. Villagran, D. G. Nocera, Chem. Commun. 2010, 46, 79;
  113. K. R. Pichaandi, P. E. Fanwick, M. M. Abu-Omar, Organometallics 2014, 33, 5089.
  114. N. G. Leonard, P. G. Williard, W. H. Bernskoetter, Dalton Trans. 2011, 40, 4300.
  115. J. A. Labinger, R. Fu, J. E. Bercaw, Organometallics 2014, 30, 6751.
  116. J. M. Meredith, R. Robinson, K. I. Goldberg, W. Kaminsky, D. M. Heinekey, Organometallics 2012, 31, 1879;
  117. M. C. Lehman, P. D. Boyle, R. D. Sommer, E. A. Ison, Organometallics 2014, 33, 5081.
  118. A. C. Atesin, J. Zhang, T. Vaidya, W. W. Brennessel, A. J. Frontier, R. Eisenberg, Inorg. Chem. 2010, 49, 4331;
  119. M. E. Slaney, D. J. Anderson, M. J. Ferguson, R. McDonald, M. Cowie, J. Am. Chem. Soc. 2010, 132, 16544;
  120. M.E.Slaney, D.J.Anderson, M.J.Ferguson, R.McDonald, M.Cowie, Organometallics 2012, 31, 2286.
  121. A. Vivancos, Y. A. Hernandez, M. Paneque, M. L. Poveda, V. Salazar, E. Alvarez, Organometallics 2015, 34, 177;
  122. D. Sieh, M. Schlimm, L. Andernach, F. Angersbach, S. Nückel, J. Schöffel, N. Šušnjar, P. Burger, Eur. J. Inorg. Chem. 2012, 444;
  123. B.J.Anding, A.Ellern, L.Keith Woo, Organometallics 2014, 33, 2219;
  124. J.-C. Wang, Z.-J. Xu, Z. Guo, Q.-H. Deng, C.-Y. Zhou, X.-L. Wan, C.-M. Che, Chem. Commun. 2012, 48, 4299.
  125. R.D.Adams, M. Chen, Organometallics 2012, 31, 6457.
  126. C .J. Durango-Garcia, J. O. C. Jimenez-Halla, M. Lopez-Cardoso, V. Montiel-Palma, M. A. Munoz-Hernandez, G. Merino, Dalton Trans. 2010, 39, 10588.
  127. A. Kruckenberg, H. Wadepohl, L. H. Gade Organometallics 2013, 32, 5153;
  128. B. J. Barrett, V. M. Iluc, Organometallics 2014, 33, 2565;
  129. L. M. Martinez-Prieto, C. Melero, D. del Rio, P. Palma, J. Campora, E. Alvarez, Organometallics 2012, 31, 1425;
  130. D. Weismann, D. Saurenz, R. Boese, D. Blaser, G. Wolmershauser, Y. Sun, H. Sitzmann, Organometallics 2011, 30, 6351;
  131. P. Nagele, U. Herrlich, F. Rominger, P. Hofmann, Organometallics 2013, 32, 181;
  132. M. Schultz, F. Eisenträger, C.Regius, F.Rominger, P.Hanno-Igels, P.Jakob, I.Gruber, P.Hofmann, Organometallics 2012, 31,207;
  133. D. Zhu, I.Thapa, I.Korobkov, S.Gambarotta, P.H.M.Budzelaar, Inorg. Chem. 2011, 50, 9879;
  134. M. Vogt, O.Rivada-Wheelaghan, M. A. Iron, G. Leitus, Y. Diskin-Posner, L. J. W. Shimon, Y. Ben-David, D. Milstein, Organometallics 2013, 32, 300; i) E. M. Matson, G. E. Martinez, A. D. Ibrahim, B.J.Jackson, J.A.Bertke, A.R.Fout, Organometallics 2015, 34, 399;
  135. K. J. Jonasson, O. F. Wendt Chem. Eur. J. 2014, 20, 11894: k)
  136. M. Abubekerov, P. L. Diaconescu, Inorg. Chem. 2015, 54, 1778.
  137. M. I. Lipschutz, X. Yang, R. Chatterjee, T. D. Tilley, J. Am. Chem. Soc. 2013, 135, 15298;
  138. M. I. Lipschutz, T.D. Tilley, Angew. Chem. Int. Ed. 2014, 53, 7290.
  139. C.-M. Lee, C.-H. Chen, F.-X. Liao, C.-H. Hu, G.-H. Lee J. Am. Chem. Soc. 2010, 132, 9256.
  140. C. Yoo, S. Oh, J. Kim, Y. Lee, Chem. Sci. 2014, 5, 3853.
  141. B. Zheng, F. Tang, J. Luo, J. W. Schultz, N. P. Rath, L. M. Mirica, J. Am. Chem. Soc. 2014, 136, 6499.
  142. C. J. Stephenson, J. P. McInnis, C. Chen, M. P. Weberski, A. Motta, M. Delferro, T. J. Marks, ACS Catalysis 2014, 4, 999;
  143. M. P. Weberski, C. Chen, M. Delferro, C. Zuccaccia, A. Macchioni, T. J. Marks, Organometallics 2012, 31, 3773;
  144. M. P. Weberski, C. Chen, M. Delferro, T. J. Marks, Chem. Eur. J. 2012, 18, 10715.
  145. T. Wiedemann, G. Voit, I. Goettker-Schnetmann, S. Mecking, J. Am. Chem. Soc. 2014, 136, 2078;
  146. A. Osichow, I. Gottker-Schnetmann, S. Mecking, Organometallics 2013, 32, 5239.
  147. Z, Chen, M. Mesgar, P. S. White, O. Daugulis, M. Brookhart, ACS Catalysis 2015, 5, 631.
  148. M. R. Radlauer, M. W. Day, T. Agapie, J. Am. Chem. Soc. 2012, 134, 1478;
  149. M. R. Radlauer, M. W. Day, T. Agapie, Organometallics 2012, 31, 2231;
  150. M. R. Radlauer, A. K. Buckley, L. M. Henling, T. Agapie, J. Am. Chem. Soc. 2013, 135, 3784.
  151. C. Tsay, J. C. Peters, Chem. Sci. 2012, 3, 1313.
  152. T. J. Schmeier, N. Hazari, C. D. Incarvito, J. A .Raskatov, Chem. Commun. 2011, 47, 1824.
  153. N. Curado, C. Maya, J. Lopez-Serrano, A. Rodríguez, Chem. Commun. 2014, 50, 15718.
  154. H. Leicht, I. Göttker-Schnetmann, S. Mecking, Angew. Chem. Int. Ed. 2013, 52, 3963;
  155. Z. Jian, P. Wucher, Stefan Mecking, Organometallics 2014, 33, 2879;
  156. P. Wucher, J. B. Schwaderer, Stefan Mecking, ACS Catalysis 2014, 4, 2672;
  157. P. Wucher, L. Caporaso, P. Roesle, F. Ragone, L. Cavallo, S. Mecking, I. Göttker- Schnetmann, Proc. Nat. Acad. Sci. USA 2011, 108, 8955;
  158. B. Neuwald, L.Caporaso, L. Cavallo, S. Mecking, J. Am. Chem. Soc. 2013, 135, 1026.
  159. a) Y. Ota, S. Ito, J. Kuroda, Y. Okumura, K. Nozaki, J. Am. Chem. Soc. 2014, 136, 11898;
  160. B. P. Carrow, K. Nozaki, J. Am. Chem. Soc. 2012, 134, 8802.
  161. a) Z. Cai, Z. Shen, X. Zhou, R. F. Jordan, ACS Catalysis 2012, 2, 1187;
  162. Z. Shen, R. F. Jordan, J. Am. Chem. Soc. 2010, 132, 52;
  163. X. Zhou, R. F. Jordan, Organometallics 2011, 30, 4632.
  164. A. Meduri, D. Cozzula, A. D'Amora, E. Zangrando, S. Gladiali, B. Milani, Dalton Trans. 2012, 41, 7474.
  165. P. Ai, A. A. Danopoulos, P. Braunstein, Dalton Trans. 2014, 43, 1957.
  166. A. Sachse, M. John, F. Meyer, Angew. Chem. Int. Ed. 2010, 49,1986.
  167. D. L. M. Suess, J. C. Peters, Chem. Commun. 2010, 46, 6554.
  168. J. Luo, J. R. Khusnutdinova, N. P. Rath, L. M. Mirica, Chem. Commun. 2012 , 48, 1532.
  169. a) J. R. Khusnutdinova, N. P. Rath, L. M. Mirica, J. Am. Chem. Soc. 2010, 132, 7303;
  170. J. R. Khusnutdinova, N. P. Rath, L. M. Mirica, J. Am. Chem. Soc. 2012, 134, 2414;
  171. F. Tang, F. Qu, J. R. Khusnutdinova, N. P. Rath, L. M.Mirica, Dalton Trans. 2012, 41, 14046.
  172. O. A. Mironov, S. M. Bischof, M. M. Konnick, B. G. Hashiguchi, V. R. Ziatdinov, W. A. Goddard, M. Ahlquist, R. A. Periana, J. Am. Chem. Soc. 2013, 135, 14644.
  173. S. E. Parker, J.Börgel, T.Ritter, J. Am. Chem. Soc. 2014, 136, 4857.
  174. N. A. Jasim, R. N. Perutz, B. Procacci, A. C. Whitwood, Chem. Commun. 2014, 50, 3914.]
  175. S. Kim, P. D. Boyle, M. S. McCready, K. R. Pellarin, R. J. Puddephatt, Chem. Commun. 2013, 49, 6421;
  176. M. Safa, M. C. Jennings, R. J. Puddephatt, Chem. Commun. 2010, 46, 2811.
  177. B. G. Cooper, C. M. Fafard, B. M. Foxman, C. M. Thomas, Organometallics 2010, 29, 5179;
  178. M.-E. Moret, D. Serra, A. Bach, P. Chen, Angew. Chem. Int. Ed. 2010, 49, 2873;
  179. D. Serra, M.-E. Moret, P. Chen, J. Am. Chem. Soc. 2011, 133, 8914.
  180. H. Braunschweig, R. Bertermann, P. Brenner, M. Burzler, R. D. Dewhurst, K. Radacki, F. Seeler, Chem. Eur. J. 2011, 17, 11828;
  181. J. Brand, H. Braunschweig, F. Hupp, A. K. Phukan,K. Radacki, S. S. Sen, Angew. Chem. Int. Ed. 2014, 53, 2240;
  182. S. Xu, F. Haeffner, B. Li, L. N. Zakharov, S.-Y. Liu, Angew. Chem. Int. Ed. 2014, 53, 6795;
  183. S. Pal, P. Y. Zavalij, A. N. Vedernikov, Chem. Commun. 2014, 50, 5376.
  184. a) O. Rivada-Wheelaghan, B. Donnadieu, C. Maya, S. Conejero, Chem. Eur. J. 2010, 16, 10323;
  185. M. Roselló-Merino, O. Rivada-Wheelaghan, M. A. Ortuño, P. Vidossich, J. Díez, A. Lledós, S. Conejero, Organometallics 2014, 33, 3746.
  186. C. Tsay, N. P. Mankad, J. C. Peters, J. Am. Chem. Soc. 2010, 132, 13975.
  187. M. L. Scheuermann, K. A. Grice, M. J. Ruppel, M. Roselló-Merino, W. Kaminsky, K. I. Goldberg, Dalton Trans. 2014, 43, 12018;
  188. A. Zucca, L. Maidich, L. Canu, G. L. Petretto, S. Stoccoro, M. A. Cinellu, G. J. Clarkson, J. P. Rourke, Chem. Eur. J. 2014, 20, 5501;
  189. J. R. Webb, A. W. Pierpont, C. Munro-Leighton, T. B. Gunnoe, T. R. Cundari, P. D. Boyle, J. Am. Chem. Soc. 2010, 132, 4520;
  190. G. C. Fortman, N. M. Scott, A. Linden, E. D. Stevens, R. Dorta, S. P. Nolan, Chem. Commun. 2010, 46, 1050.
  191. Y. Tulchinsky, S. Kozuch, P. Saha, M. Botoshansky, L. J. W. Shimon, M. Gandelman, Chem. Sci. 2014, 5, 1305.
  192. R. Eujen, B. Hoge, D. J. Brauer, Inorg. Chem. 1997, 36, 1464.
  193. S. H. Bertz, R. A. Hardin, T. J. Heavey, D. S. Jones, T. B. Monroe, M. D. Murphy, C. A. Ogle, T. N. Whaley, Chem. Eur. J. 2013, 31, 10138.
  194. G. Ma, M. J. Ferguson, R. McDonald, R. G.Cavell, Organometallics 2010, 29, 4251.
  195. A. Venugopal, A. P. Shaw, K. W. Törnroos, R. H. Heyn, M. Tilset, Organometallics 2011, 30, 3250;
  196. E. Langseth, C. H. Görbitz, R. H. Heyn, M. Tilset, Organometallics 2012, 31, 6567;
  197. E. Langseth, M. L. Scheuermann, D. Balcells, W. Kaminsky, K. Goldberg, O. Eisenstein, R. H. Heyn, M. Tilset, Angew. Chem. Int. Ed. 2013, 52, 1660.
  198. a) E. Tkatchouk, N. P. Mankad, D. Benitez, W. A. Goddard, F. D. Toste, J. Am. Chem. Soc. 2011, 133, 14293;
  199. N. P. Mankad, F. D. Toste, J. Am. Chem. Soc. 2010, 132, 12859.
  200. M. T.Johnson, J. M. J. van Rensburg, M. Axelsson, M. S. G. Ahlquist, O. F. Wendt, Chem. Sci. 2011, 2, 2373.
  201. V. J. Scott, J. A. Labinger, J. E. Bercaw, Organometallics 2010, 29, 4090.
  202. M. Stollenz, N. Bhuvanesh, J. H. Reibenspies, J. A. Gladysz, Organometallics 2011, 30, 6510.
  203. A. Venugopal, M. K. Ghosh, H. Jürgens, K.W.Törnroos, O. Swang, M. Tilset, R. H. Heyn, Organometallics 2010, 29, 2248.
  204. G. I. Zharkova, I. A. Baidina, T. S. Yudanova, Polyhedron 2010, 29, 1049.
  205. R. Parkhomenko, A. Alexeyev, N. Morozova, I. Igumenov, J. Coord. Chem. 2012, 65, 3227.
  206. M. Fernández-Espada, J. Campos. J. López-Serrano, M. L. Poveda, Angew. Chem. Int. Ed. 2015 DOI: 10.1002/ange.201508931.
  207. P. Braunstein, N. M. Boag, Angew. Chem. Int. Ed. 2001, 40, 2427.
  208. G. Parkin, Struct. Bond. 2010, 136, 113.
  209. Y.-X. Chen, C. L. Stern, S. Yang, T. J. Marks, J. Am. Chem. Soc. 1996, 118, 12451.
  210. C. Wang, M. van Meurs, L. P. Stubbs, B.-Y. Tay, X.-J. Tan, S. Aitipamula, J. Chacko, H.-K. Luo, P.-K. Wong, S. Ye, Dalton Trans. 2010, 39, 807.
  211. A. P. Duncan, S. M. Mullins, J. Arnold, R. G. Bergman, Organometallics 2001, 20, 1808.
  212. M. E. García, A. Ramos, M. A. Ruiz, M. Lanfranchi, L. Marchio, Organometallics 2007, 26, 6197.
  213. C. Ni, P. P. Power, Organometallics 2009, 28, 6541.
  214. R. A. Heintz, R. L. Ostrander, A. L. Rheingold, K. H. Theopold, J. Am. Chem. Soc. 1994, 116, 11387.
  215. B. E. Bursten, R. H. Cayton, Organometallics 1986, 5, 1051.
  216. M. Brookhart, M. L. H. Green, G. Parkin, Proc. Nat. Ac. Sci. USA 2007, 104, 6908.
  217. W. Scherer, G. S. McGrady, Angew. Chem. Int. Ed. 2004, 43, 1782.
  218. M. Etienne, J. E. McGrady, F. Maseras, Coord. Chem. Rev. 2009, 253, 635;
  219. D. A. Pantazis, J. E. McGrady, M. Besora, F. Maseras, M. Etienne, Organometallics 2008, 27, 1128.
  220. J. R. Wigginton, S. J. Trepanier, R. McDonald, M. J. Ferguson, M. Cowie, Organometallics 2005, 24, 6194.
  221. J. W. Park, P. B. Mackenzie, W. P. Schaefer, R. H. Grubbs, J. Am. Chem. Soc. 1986, 108, 6402.
  222. M.-H. Baik, R. A. Friesner, G. Parkin, Polyhedron 2004, 23, 2879.
  223. J. Ho Shin, G. Parkin, Chem. Commun. 1998, 1273.
  224. K. E. Allen, J. Campos, O. Daugulis, M. Brookhart, ACS Catal. 2015, 5, 456;
  225. D. Guironnet, L. Caporaso, B. Neuwald, I. Goettker- Schnetmann, L. Cavallo, S. Mecking, J. Am. Chem. Soc. 2010, 132, 4418;
  226. C. Chen, S. Luo, R. F. Jordan, J. Am. Chem. Soc. 2010, 132, 5273;
  227. S. M. Baldwin, J. E. Bercaw, H. H. Brintzinger, J. Am. Chem. Soc. 2010, 132, 13969;
  228. J. C. Milsmann, K. Wieghardt, J. Am. Chem. Soc. 2010, 132, 15046;
  229. J. W. Tye, J. F. Hartwig, J. Am. Chem. Soc. 2009, 131, 14703.
  230. H. C. Clark, C.R. C. Milne, C. S. Wong, J. Organomet. Chem. 1977, 136, 265;
  231. L. Canovese, F. Visentin, G. Chessa, P. Uguagliati, C. Santo, A. Dolmella, Organometallics 2005, 24, 3297.
  232. a) L. Canovese, F. Visentin, G. Chessa, P. Uguagliati, G. Bandoli, Organometallics 2000, 19, 1461;
  233. L. Canovese, F. Visentin, G. Chessa, P. Uguagliati, C. Santo, G. Bandoli, L. Maini, Organometallics 2003, 22, 3230;
  234. L. Canovese, F. Visentin, G. Chessa, C. Santo, P. Uguagliati, G. Bandoli, J. Organomet. Chem. 2002, 650, 43.
  235. V.P. Boyarskiy, N.A. Bokach, K.V. Luzyanin, V.Y. Kukushkin, Chem. Rev. 2015, 115, 2698;
  236. J. Sánchez-Nieves, P. Royo, M. A. Pellinghelli, A. Tiripicchio, Organometallics 2000, 19, 3161;
  237. P. Kofod, H. Pernille, L. Sine, Inorg. Chem. 2003, 42, 244;
  238. G. R. Owen, R. Vilar, A. J. P. White, D. J. Williams, Organometallics 2002, 21, 4799;
  239. A. C. Badaj, G. G. Lavoie, Organometallics 2013, 32, 4577.
  240. a) L. Pospíšil, M. Hromadová, J. Fiedler, C. Amatore, J.-N. Verpeaux, J. Organomet. Chem. 2003, 668, 9;
  241. J. L. Davis, B. A. Arndtsen, Organometallics 2000, 19, 4657;
  242. Y. Kataoka, A. Shibahara, T. Yamagata, K. Tani, Organometallics 2001, 20, 2431;
  243. K. R. Reddy, K. Surekha, G.-H. Lee, S.-M. Peng, J.-T. Chen, S.-T. Liu, Organometallics, 2001, 20, 1292;
  244. A. Bastero, A. Ruiz, C. Claver, B. Milani, E. Zangrando, Organometallics 2002, 21, 5820;
  245. J.-I. Setsune, T. Yamauchi, S. Tanikawa, Y. Hirose, J.-Y. Watanabe, Organometallics 2004, 23, 6058;
  246. P. Braunstein, C. Frison, X. Morise, Angew. Chem. Int. Ed. 2000, 39, 2867;
  247. J. Ledford, C. S. Shultz, D. P. Gates, P. S. White, J. M. DeSimone, M. Brookhart, Organometallics 2001, 20, 5266.
  248. D. J. Darensbourg, R. K. Hanckel, C. G. Bauch, M. Pala, D. Simmons, J. N. White, J. Am. Chem. Soc. 1985, 107, 7463;
  249. J. Sánchez-Nieves, P. Royo, J. Organomet. Chem. 2001, 621, 299;
  250. N. P. Mankad, T. G. Gray, D. S. Laitar, J. P. Sadighi, Organometallics 2004, 23, 1191;
  251. R. Johansson, M. Jarenmark, O. F. Wendt, Organometallics 2005, 24, 4500;
  252. D. J. Darensbourg, G. Grötsch, P. Wiegreffe, A. L. Rheingold, Inorg. Chem. 1987, 26, 3827-3830;
  253. S. Sakaki, K. Ohkubo, Organometallics 1989, 8, 2970.
  254. D. P. Gates, P. S. White, M. Brookhart, Chem. Commun. 2000, 47.
  255. A. Caballero, P. J. Pérez, Chem. Soc. Rev. 2013, 42, 8809;
  256. N. J. Gunsalus, M. M. Konnick, B. G. Hashiguchi, R. A. Periana, Isr. J. Chem. 2014, 54, 1467; c) Methane Functionalization in 'Activation of Small Molecules: Organometallic and Bioinorganic Perspectives', B. L. Conley, W. J. Tenn, K. J. Young, S. Ganesh, S. Meier, V. Ziatdinov, O. Mironov, J. Oxgaard, J. Gonzales, W. A. Goddard, R. A. Periana, John Wiley and Sons, 2006.
  257. a) L. Boisvert, M. C. Denney, S. K. Hanson, K. I. Goldberg, J. Am. Chem. Soc. 2009, 131, 15802;
  258. K. A. Grice, K. I. Goldberg, Organometallics 2009, 28, 953;
  259. L. Boisvert, K. I. Goldberg, Acc. Chem. Res. 2013, 45, 899.
  260. R. A.Taylor, D. J. Law, G. J. Sunley, A. J. P. White, G. J. P. Britovsek, Ang. Chem. Int. Ed. 2009, 48, 5900;
  261. A. R. Petersen, R. A. Taylor, I. Vicente-Hernández, P. R. Mallender, H. Olley, A. J. P. White, G. J. P. Britovsek, J. Am. Chem. Soc. 2014, 136, 14089.
  262. M. C. Lehman, D. R. Pahls, J. M. Meredith, R. D. Sommer, D. M. Heinekey, T. R. Cundari, E. A. Ison, J. Am. Chem. Soc. 2015, 137, 3574.
  263. S. Pal, A. N. Vedernikov, Dalton Trans. 2012, 41, 8116.
  264. J. Mei, D. B. Pardue, S. E. Kalman, T. B. Gunnoe, T. R. Cundari, M. Sabat, Organometallics 2014, 33, 5597.
  265. a) B. M. Prince, T. B. Gunnoe, T. R. Cundari, Dalton Trans. 2014, 43, 7608;
  266. C. S. Slone, D. A. Weinberger, C. A. Mirkin, Progr. Inorg. Chem. 1999, 48, 233;
  267. P. Braunstein, F. Naud, Angew. Chem. Int. Ed. 2001, 40, 680;
  268. R. Lindner, B. van den Bosch, M. Lutz, J. N. H. Reek, J. I. van der Vlugt, Organometallics 2011, 30, 499.
  269. M. J. Pouy, E. M. Milczek, T. M. Figg, B. M. Otten, B. M. Prince, T. B. Gunnoe, T. R. Cundari, J. T. Groves, J. Am. Chem. Soc. 2012, 134, 12920.
  270. A. L. Johnson, N. Hollingsworth, G. Kociok-Kohn, K. C. Molloy, Angew. Chem. Int. Ed. 2012, 51, 4108.
  271. R. F. Jordan, W. E. Dasher, S. F. Echols, J. Am. Chem. Soc. 1986, 108, 1718;
  272. R. F. Jordan, Adv. Organomet. Chem. 1991, 32, 325;
  273. H. H. Brintzinger, D. Fischer, R. Mülhaupt, B. Rieger, R.M. Waymouth, Angew. Chem. Int. Ed. 1995, 34, 1143;
  274. M. Bochmann J. Chem. Soc. Dalton Trans. 1996, 255;
  275. E. Y. X. Chen, T. J. Marks, Chem. Rev. 2000, 100, 1391.
  276. a) X. Xu, R. Frçhlich, C.G. Daniliuc, G. Kehr, G. Erker, Chem. Commun. 2012, 48, 6109;
  277. X. Xu, G. Kehr, C. G. Daniliuc, G. Erker, J. Am. Chem. Soc. 2013, 135, 6465;
  278. A. D. Horton, A. G. Orpen, Organometallics 1991, 10, 3910;
  279. A. D. Horton, A. G. Orpen, Organometallics 1992, 11, 8.
  280. a) X. Xu, G. Kehr, C. G. Daniliuc, G. Erker, Angew. Chem, Int. Ed. 2013, 52, 13629;
  281. X. Xu, G. Kehr, C. G. Daniliuc, G. Erker, J. Am. Chem. Soc. 2013, 135, 6465;
  282. X. Xu, G. Kehr, C. G. Daniliuc, G. Erker, J. Am. Chem. Soc. 2014, 136, 12431.
  283. a) B. Wrackmeyer, Coord. Chem. Rev. 1995, 145, 125;
  284. B. Wrackmeyer, Heteroat. Chem. 2006, 17, 188.
  285. A. Vigalok, D. Milstein, Organometallics 2000, 19, 2341.
  286. C. K. Rofer-DePoorter, Chem. Rev. 1981, 81, 447;
  287. A. Y. Khodakov, W. Chu, P. Fongarland, Chem. Rev. 2007, 107, 1692;
  288. M. West, A. J. M. Miller, J. A. Labinger, J. E. Bercaw, Coord. Chem. Rev. 2011, 255, 881.
  289. A. Hazari, J. A. Labinger, J. E. Bercaw, Angew. Chem. Int. Ed. 2012, 51, 8268.
  290. J. L. Smeltz, P. D. Boyle, E. A. Ison, J. Am. Chem. Soc. 2011, 133, 13288.
  291. F. Rekhroukh, R. Brousses, A. Amgoune, D. Bourissou, Angew. Chem. Int. Ed. 2015, 54, 1266.
  292. a) R. H. Crabtree, Chem. Rev. 1995, 95, 987;
  293. J. H. Lunsford, Angew. Chem. Int. Ed. 1995, 34, 970;
  294. A. Holmen, Catal. Today 2009, 142, 2;
  295. M. C. Alvarez-Galvan, N. Moto, M. Ojeda, S. Rojas, R. M. Navarro, J. L. G. Fierro, Catal. Today 2011, 171, 15;
  296. C. Hammond, S. Conrad, I. Hermans, ChemSusChem 2012, 5, 1668;
  297. G. A. Martin, C. Mirodatos, Fuel Process. Technol. 1995, 42, 179;
  298. G. A. Olah, Acc. Chem. Res. 1987, 20, 422;
  299. M. P. Lanci, M. S. Remy, W. Kaminsky, J. M. Mayer, M. S. Sanford, J. Am. Chem. Soc. 2009, 131, 15618; i) D. M. Crumpton, K. I. Goldberg, J. Am. Chem. Soc. 2000, 122, 962;
  300. S. M. Kloek, K. I. Goldberg, J. Am. Chem. Soc. 2007, 129, 3460.
  301. M. S. Remy, T. Cundari, M. S. Sanford, Organometallics 2010, 29, 1522.
  302. M. P. Lanci, M. S. Remy, W. Kaminsky, J. M. Mayer, M. S. Sanford, J. Am. Chem. Soc. 2009, 131, 15618.
  303. M. D. Lotz, M. S. Remy, D. B. Lao, A. Ariafard, B. F. Yates, A. J. Canty, J. M. Mayer, M. S. Sanford, J. Am. Chem. Soc. 2014, 136, 8237.
  304. A. Yamamoto, T. Ikariya, J. Organomet. Chem. 1976, 120, 257.
  305. H. Xu, W. H. Bernskoetter, J. Am. Chem. Soc. 2011, 133, 14956.]
  306. A. Vigalok, Chem. Eur. J. 2008, 14, 5102;
  307. A. Vigalok, A. W. Kaspi, Top. Organomet. Chem. 2010, 31, 19;
  308. X. Jiang, H. Liu, Z. Gu, Asian J. Org. Chem. 2012, 1, 16.
  309. A. E. Shilov, G. B. Shul'pin, Chem. Rev. 1997, 97, 2879.
  310. G. A. Luinstra, L. Wang, S. S. Stahl, J. A. Labinger, J. E. Bercaw, J. Organomet. Chem. 1995, 504, 75;
  311. G. A. Luinstra, J. A. Labinger, J. E. Bercaw, J. Am. Chem. Soc. 1993, 115, 3004.
  312. a) K. I. Goldberg, J. Y. Yan, E. L. Winter, J. Am. Chem. Soc. 1994, 116, 1573;
  313. K. I. Goldberg, J. Y. Yan, E. M. Breitung, J. Am. Chem. Soc. 1995, 117, 6889.
  314. M. Feller, A. M. Iron, L. J. W. Shimon, Y. Diskin-Posner, G. Leitus, D. Milstein, J. Am. Chem. Soc. 2008, 130, 14374;
  315. C. M. Frech, D. Milstein, J. Am. Chem. Soc. 2006, 128, 12434.
  316. P. W. Vickers, J. M. Pearson, T. Ghaffar, H. Adams, A. Haynes, J. Phys. Org. Chem. 2004, 17, 1007.
  317. M. E. O'Reilly, D. R. Pahls, J. R.Webb, N. C. Boaz, S. Majumdar, C. D. Hoff, J. T. G., T. R. Cundari, T. B. Gunnoe, Dalton Trans. 2014, 43, 8273.
  318. M. Feller, Y. Diskin-Posner, G. Leitus, L. J. W. Shimon, D. Milstein, J. Am. Chem. Soc. 2013, 135, 11040.
  319. B. L. Small, Acc. Chem. Res. 2015, 48, 2599.
  320. a) X. Yang, C. L. Stern, T. J. Marks, J. Am. Chem. Soc. 1991, 113, 3623;
  321. X. Yang, C. L. Stern, T. J. Marks, J. Am. Chem. Soc. 1994, 116, 10015.
  322. F. Sauriol, J. F. Sonnenberg, S. J. Chadder, A. F. Dunlop-Brière, M. C. Baird, P. H. M. Budzelaar J. Am. Chem. Soc. 2010, 132, 13357;
  323. J. C.W. Chien, W. M. Tsai, M. D. Rausch, J. Am. Chem. Soc. 1991, 113, 8570;
  324. M. Bochmann, S. J. Lancaster, J. Organomet. Chem. 1992, 434, C1.
  325. T. S. Chong, T. S. Chwee, W. K. Leong, M. W. Wong, W. Y. Fan, J. Organomet. Chem. 2006, 691, 687.
  326. W. H. Bernskoetter, S. K. Hanson, S. K. Buzak, Z. Davis, P. S. White, R. Swartz, K. I. Goldberg, M. Brookhart, J. Am. Chem. Soc. 2009, 131, 8603.
  327. M. A. Iron, H. C. Lo, J. M. L. Martin, E. Keinan, J. Am. Chem. Soc. 2002, 124 , 7041.
  328. G. S. Hill, L. M. Rendina, R. J. Puddephatt, Organometallics 1995, 14, 4966;
  329. J. Parmene, I. Ivanovic-Burmazovic, M. Tilset, R. van Eldik, Inorg. Chem. 2009, 48, 9092;
  330. R. Romeo, M. R. Plutino, L. I. Elding, Inorg. Chem. 1997, 36, 5909;
  331. S. S. Stahl, J. A. Labinger, J. E. Bercaw, J. Am. Chem. Soc. 1995, 117, 9371;
  332. B. J. Wik, I. Ivanovic- Burmazovic, M. Tilset, R. van Eldik, Inorg. Chem. 2006, 45, 3613;
  333. B. J. Wik, M. Lersch, M. Tilset, J. Am. Chem. Soc. 2002, 124, 12116.
  334. J. E. Bercaw, G. S. Chen, J. A. Labinger, B.-L. Lin, Organometallics 2010, 29, 4354.
  335. J. E. Bercaw, G. S. Chen, J. A. Labinger, B.-L. Lin, J. Am. Chem. Soc. 2008, 130, 17654;
  336. V. J. Scott, J. A. Labinger, J. E. Bercaw, Organometallics 2011, 30, 4374.
  337. R. N. Perutz, S. Sabo-Etienne, Angew. Chem. Int. Ed. 2007, 46, 2578.
  338. A. Rudolph, M. Lautens, Angew. Chem. Int. Ed. 2009, 48, 2656;
  339. W. Affo, H. Ohmiya, T. Fujioka, Y. Ikeda, T. Nakamura, H. Yorimitsu, K. Oshima, Y. Imamura, T. Mizuta, K. Miyoshi, J. Am. Chem. Soc. 2006, 128, 8068;
  340. J. Waser, B. Gaspar, H. Nambu, E. M. Carreira, J. Am. Chem. Soc. 2006, 128, 11693;
  341. G. D. Jones, J. L. Martin, C. McFarland, O. R. Allen, R. E. Hall, A. D. Haley, R. J. Brandon, T. Konovalova, P. J. Desrochers, P. Pulay, D. A. Vicic, J. Am. Chem. Soc. 2006, 128, 13175;
  342. R. Poli, Angew. Chem., Int. Ed. 2006, 45, 5058;
  343. K. M. Smith, W. S. McNeil, A. S. Abd-El-Aziz, Macromol. Chem. Phys. 2010, 211, 10;
  344. F. di Lena, K. Matyjaszewski, Prog. Polym. Sci. 2010, 35, 959;
  345. O. Vechorkin, V. Proust, X. Hu, J. Am. Chem. Soc. 2009, 131, 9756;
  346. V. B. Phapale, E. Bunuel, M. García-Iglesias, D. J. Cárdenas, Angew. Chem., Int. Ed. 2007, 46, 8790;
  347. P. M. Lundin, G. C. Fu, J. Am. Chem. Soc. 2010, 132, 11027.
  348. K. C. MacLeod, J. L. Conway, B. O. Patrick, K. M. Smith, J. Am. Chem. Soc. 2010, 132, 17325.
  349. M. Yu, X. Fu, J. Am. Chem. Soc. 2011, 133, 15926.
  350. R. R. Schrock, P. R. Sharp, J. Am. Chem. Soc. 1978, 100, 2389.
  351. D. B. Jacobson, J. R. Gord, B. S. Freiser, Organometallics 1989, 8, 2957.
  352. D. Y. Dawson, J. Arnold, Organometallics 1997, 16, 1111.
  353. K. Searles, B. Pinter, C.-H. Chen, D. J. Mindiola, Organometallics 2014, 33, 4192.
  354. K. Searles, K. Keijzer, C.-H. Chen, M.-H. Baik, D. J. Mindiola, Chem Commun. 2014, 50, 6267.
  355. M. Kamitani, B. Pinter, C.-H. Chen, M. Pink, D. J. Mindiola, Angew. Chem. Int. Ed. 2014, 53, 10913;
  356. W. Weng, L. Yang, B. M. Foxman, O. V. Ozerov, Organometallics 2004, 23, 4700;
  357. A. J. Downs, G. Dierker, J. C. Green, T. M. Greene, G. S. McGrady, L. J. Morris, W. Scherer, P. Sirsch, J. Chem. Soc., Dalton Trans. 2002, 3349;
  358. L. J. Morris, A. J. Downs, J. C. Green, T. M. Greene, S. J. Teatc, S. Parsons, J. Chem. Soc., Dalton Trans. 2002, 3142;
  359. L. R. Chamberlain, I. P. Rothwell, J. C. Huffmad, J. Am. Chem. Soc. 1986, 108, 1502;
  360. L. R. Chamberlain, A. P. Rothwell, I. P. Rothwell, J. Am. Chem. Soc. 1984, 106, 1847;
  361. P. J. Chirik, D. L. Zubris, L. J. Ackerman, L. M. Henling, M. W. Day, J. E. Bercaw, Organometallics 2003, 22, 172;
  362. L. C. H. Gerber, L. A. Watson, S. Parkin, W. Weng, B. M. Foxman, O. V. Ozerov, Organometallics 2007, 26, 4866.
  363. M. D. Fryzuk, K. Joshi, R. K. Chadha, S. J. Rettig, J. Am. Chem. Soc. 1991, 113, 8724;
  364. M. D. Fryzuk, K. Joshi, R. K. Chadha, J. Am. Chem. Soc. 1989, 11, 4498;
  365. L. J. Morris, A. J. Downs, T. M. Greene, G. S. McGrady, W. A. Herrmann, P. Sirsch, W. Scherer, O. Gropen, Organometallics 2001, 20, 2344.
  366. Y. Chen, E. Callens, E. Abou-hamad, J.-M. Basset, J. Organomet. Chem. 2013, 744, 3.
  367. M. K. Samantaray, E. Callens, E. Abou-Hamad, A. J. Rossini, C. M. Widdifield, R. Dey, L. Emsley, J.-M. Basset, J. Am. Chem. Soc. 2014, 136, 1054.
  368. a) E. Lu, Q. Zhou, Y. Li, J. Chu, Y. Chen, X. Leng, J. Sun, Chem. Commun. 2012, 48, 3403;
  369. B. F. Wicker, H. Fan, A. K. Hickey, M. G. Crestani, J. Scott, M. Pink, D. J. Mindiola, J. Am. Chem. Soc. 2012, 134, 20081.
  370. C. Boulho, P. Oulie, L. Vendier, M. Etienne, V. Pimienta, A. Locati, F. Bessac, F. Maseras, D. A. Pantazis, J. E. McGrady, J. Am. Chem. Soc. 2010, 132, 14239.
  371. J. R. Krumper, R. L. Martin, P. J. Hay, C. M. Yung, J. Veltheer, R. G. Bergman, J. Am. Chem. Soc. 2004, 126, 14804;
  372. R. H. Hooker, K. A.
  373. Mahmoud, A. J. Rest, J. Organomet. Chem. 1991, 419, 101;
  374. K. A. Mahmoud, A. J. Rest, H. G. Alt, J. Chem. Soc., Chem. Commun. 1983, 18, 1011;
  375. A. van Asselt, B. J. Burger, V. C. Gibson, J. E. Bercaw., J. Am. Chem. Soc. 1986, 108, 5347;
  376. D. M. Antonelli, W. P. Schaefer, G. Parkin, J. E. Bercaw, J. Organomet. Chem. 1993, 462, 213;
  377. A. A. Van, B. J. Burger, V. C. Gibson, J. E. Bercaw, J. Am. Chem. Soc. 1986, 108, 5347;
  378. H.-G. Cho, L. Andrews, Inorg.Chem. 2005, 44, 979;
  379. H.-G.
  380. Cho, L. Andrews, J. Am. Chem. Soc. 2004, 126, 10485.
  381. W. Buchowicz, B. Herbaczyńska, L. B. Jerzykiewicz, T. Lis, S. Pasynkiewicz, A. Pietrzykowski, Inorg. Chem. 2012, 51, 8292.
  382. a) Boronic Acids: Preparation and Applications in Organic Synthesis Medicine and Materials (Ed.: D. G. Hall), Wiley-VCH, Weinheim, 2011;
  383. Metal Catalyzed Cross-Coupling Reactions (Ed.: F. Diederich, P. J. Stang), Wiley-VCH,Weinheim, 2008;
  384. I. A. I. Mkhalid, J. H. Barnard, T. B. Marder, J. M. Murphy, J. F. Hartwig, Chem. Rev. 2010, 110, 890.
  385. M. Beller, A. Zapf, W. Magerlein, Chem. Eng. Technol. 2001, 24, 575.
  386. a) B. D. Sherry, A. Fürstner, Acc. Chem. Res. 2008, 41, 1500;
  387. A. Fürstner, R. Martin, Chem. Lett. 2005, 34, 624;
  388. W. M. Czaplik, M. Mayer, J. Cvengros, A. J. Wangelin, ChemSusChem 2009, 2, 396;
  389. R. Jana, T. P. Pathak, M. S. Sigman, Chem. Rev. 2011, 111, 1417;
  390. M. Kuzmina, A. K. Steib, D. Flubacher, P. Knochel, Org. Lett. 2012, 14, 4818;
  391. R. B. Bedford, M. Betham, D. W. Bruce, A. A. Danopoulos, R. M. Frost, M. Hird, J. Org. Chem. 2006, 71, 1104;
  392. R. B. Bedford, P. B. Brenner, E. Carter, T. W. Carvell, P. M. Cogswell, T. Gallagher, J. N. Harvey, D. M. Murphy, E. C. Neeve, J. Nunn, D. R. Pye, Chem. Eur. J. 2014, 20, 7935.
  393. M. Tamura, J. K. Kochi, J. Am. Chem. Soc. 1971, 93, 1487;
  394. M. Tamura, J. K. Kochi, J. Organomet. Chem. 1971, 31, 289.
  395. A. Fürstner, H. Krause, C. W. Lehmann, Angew. Chem., Int. Ed. 2006, 45, 440;
  396. A. Fürstner, R. Martin, H. Krause, G. Seidel, R. Goddard, C. W. Lehmann, J. Am. Chem. Soc. 2008, 130, 8773.
  397. M. H. Al-Afyouni, K. L. Fillman, W. W. Brennessel, M. L. Neidig, J. Am. Chem. Soc. 2014, 136, 15457.
  398. a) Organocopper Reagents: A Practical Approach (The Practical Approach in Chemistry Series). Ed. Richard J. K. Taylor, Oxford University Press, 1995;
  399. Modern Organocopper Chemistry, Ed. N. Krause, Wiley-VCH, 2002.
  400. M. John, C. Auel, C. Behrens, M. Marsch, K. Harms, F. Bosold, R. M. Gschwind, P. R. Rajamohanan, G. Boche, Chem. Eur. J. 2000, 6, 3060.
  401. S. H. Bertz, R. A. Hardin, M. D. Murphy, C. A. Ogle, J. D. Richter, A. A. Thomas, Angew. Chem. Int. Ed. 2012, 51, 2681;
  402. S. H. Bertz, R. A. Hardin, C. A. Ogle, J. Am. Chem. Soc. 2013, 135, 9656;
  403. S. H. Bertz, Y. Moazami, M. D. Murphy, C. A. Ogle, J. D. Richter, A. A. Thomas, J. Am. Chem. Soc. 2010, 132, 9549.
  404. S. H. Bertz, R. A. Hardin, T. J. Heavey, C. A. Ogle, Angew. Chem. Int. Ed. 2013, 52, 10250.
  405. a) P. A. Wender, J. M. Nuss, D. B. Smith, A. Suárez-Sobrino, J. Vagberg, D. Decosta, J. Bordner, J. Org. Chem. 1997, 62, 4908;
  406. P. A. Wender, N. C. Ihle, J. Am. Chem. Soc. 1986, 108, 4678;
  407. P. A. Wender, T. E. Jenkins, J. Am. Chem. Soc. 1989, 111, 6432;
  408. P. A. Wender, T. E. Smith, J. Org. Chem. 1995, 60, 2962;
  409. P. A. Wender, T. E. Jenkins, S. Suzuki, J. Am. Chem. Soc. 1995, 117, 1843;
  410. M. Lautens, W. Klute, W. Tam, Chem. Rev. 1996, 96, 49;
  411. P. Bhatarah, E. H. Smith, J. Chem. Soc., Perkin Trans. 1992, 1, 2163;
  412. Y. Sato, T. Nishimata, M. Mori, J. Org. Chem. 1994, 59, 6133.
  413. For representative examples, see: a) J. Montgomery, Acc. Chem. Res. 2000, 33, 467;
  414. S. Ikeda, Acc. Chem. Res. 2000, 33, 511;
  415. Y. Sato, M. Takimoto, M. Mori, J. Am. Chem. Soc. 2000, 122, 1624;
  416. M. Kimura, H. Fujimatsu, A. Ezoe, K. Shibata, M. Shimizu, S. Matsumoto, Y. Tamaru, Angew. Chem., Int. Ed. 1999, 38, 397;
  417. A. Ezoe, M. Kimura, T. Inoue, M. Mori, Y. Tamaru, Angew. Chem., Int. Ed. 2002, 41, 2784;
  418. K. M. Miller, W.-S. Huang, T. F. Jamison, J. Am. Chem. Soc. 2003, 125, 3442;
  419. S. J. Patel, T. F. Jamison, Angew. Chem., Int. Ed. 2003, 42, 1364;
  420. J. Montgomery, Angew. Chem., Int. Ed. 2004, 43, 3890.
  421. H. P. Hratchian, S. K. Chowdhury, V. M. Gutiérrez-García, K. K. D. Amarasinghe, M. J. Heeg, H. B. Schlegel, J. Montgomery, Organometallics 2004, 23, 4636.
  422. S. Ogoshi, M. Ueta, T. Arai, H. Kurosawa, J. Am. Chem. Soc. 2005, 127, 12810.
  423. K. Ziegler, E. Holzkamp, H. Breil, H. Martin, Angew. Chem. 1955, 67, 541.
  424. a) K. Ziegler, H. G. Gellerr, K. Zosel, E. Holzkamp, J. Sckneider, M. Sdfl, W.-R. Kroll, Liebigs Ann. Chem. 1960, 629, 121;
  425. K. Ziegler, H.- G. Gellert, E. Holzkamp, G. Wilke, E. W Duck, W.-R. Kroll, Liebigs Ann. Chem. 1960, 629, 172.
  426. G. Wilke, Angew. Chem., Int. Ed., 2003, 42, 5000.
  427. G. Wilke, Angew. Chem., Int. Ed. 1988, 27, 185;
  428. K. Fischer, K. Jonas, P. Misbach, R. Stabba G. Wilke, Angew. Chem., Int. Ed. 1973, 12, 943;
  429. K. R. Porschke, K. Jonas, G. Wilke, R. Benn, R. Mynott, R. Goddard, C. Kruger, Chem. Ber. 1985, 118, 275;
  430. K. R. Porschke, K. Jonas, G. Wilke, Chem. Ber., 1988, 121, 1913;
  431. W. Kaschube, K. R. Porschke, K. Angermund, C. Kruger, G. Wilke, Chem.Ber., 1988, 121, 1921;
  432. K. R. Porschke, G. Wilke, J. Organomet. Chem. 1988, 349, 257;
  433. J. J. Eisch, X. Ma, M. Singhand, G. Wilke, J. Organomet. Chem. 1997, 527, 301;
  434. J. J. Eisch, S. R. Sexsmithand, K. C. Fichter, J. Organomet. Chem. 1990, 382, 273.
  435. Z. Weng, S. Teo, L. L. Kohb, T. S. A. Hor Chem. Commun. 2006, 1319.
  436. a) Eds.: A. de Meijere, F. Diederich, Metal-Catalyzed Cross- Coupling Reactions, 2nd ed.; Wiley-VCH:Weinheim, 2004. b) D. C. Billington in Comprehensive Organic Synthesis, Vol. 3 (Ed. G. Pattenden), Pergamon Press, Oxford, 1991, p. 413.
  437. a) P. Ribagnac, M. Blug, J. Villa-Uribe, X.-F. Le Goff, C. Gosmini, N. ́ Mezailles, Chem. Eur. J. 2011, 17, 14389;
  438. J. Li, L. Jin, C. Liu, A. Lei, Chem. Commun. 2013, 49, 9615;
  439. J. Li, L. Jin, C. Liu, A. Lei, Org. Chem. Front. 2014, 1, 50;
  440. Y. Yang, T. J. L. Mustard, P. H.-Y.Cheong, S. L. Buchwald, Angew. Chem. Int. Ed. 2013, 52, 14098;
  441. L. Jin, A. Lei, Org. Biomol. Chem. 2012, 10, 6817. (f) C. Valente, S. Çalimsiz, K. H. Hoi, D. Mallik, M. Sayah, M. G. Organ, Angew. Chem. Int. Ed. 2012, 51, 3314.
  442. a) M. García-Melchor, B. Fuentes, A. Lledós, J. A. Casares, G. Ujaque, P. Espinet, J. Am. Chem. Soc. 2011, 133, 13519.; b) J. del Pozo, E. Gioria, J. A. Casares, R. Álvarez, P. Espinet, Organometallics 2015, 34, 3120.
  443. S. E. Smith, J. M. Sasaki, R. G. Bergman, J. E. Mondloch, R. G. Finke J. Am. Chem. Soc. 2008, 130, 1839.
  444. J. D. Prantner, W. Kaminsky, K. I. Goldberg, Organometallics 2014, 33, 3227;
  445. A, V. Sberegaeva, W.-G. Liu, R. J. Nielsen, W. A. Goddard, A. N. Vedernikov, J. Am. Chem. Soc. 2014, 136, 4761;
  446. E. Khaskin, P. Y. Zavalij, A. N. Vedernikov, J. Am. Chem. Soc. 2008, 130, 10088.
  447. H. Xu, P. G. Williard, W. H. Bernskoetter, Organometallics 2013, 32, 798.
  448. H. K. Sharma, R. Arias-Ugarte, A. Metta-Magana, K. H. Pannell, Chem. Commun. 2010, 46, 4586.
  449. J. R. Torkelson, F. H. Antwi-Nsiah, R. McDonald, M. Cowie, J. G. Pruis, K. J. Jalkanen, R. L. DeKock, J. Am. Chem. Soc. 1999, 121, 3666.
  450. R. G. Samant, S. J. Trepanier, J. R. Wigginton, L. Xu, M. Bierenstiel, R. McDonald, M. J. Ferguson, M. Cowie, Organometallics 2009, 28, 3407.
  451. a) D. H. Hamilton, J. R. Shapley, Organometallics 2000, 19, 761;
  452. R. B. Calvert, J. R. Shapley, J. Am. Chem. Soc. 1977, 99, 5225;
  453. E. L. Muetterties, Angew. Chem. Int. Ed. 1978, 17, 545;
  454. R. B. Calvert, J. R. Shapley, J. Am. Chem. Soc. 1978, 100, 7726.
  455. J. R. Wigginton, S. J. Trepanier, R. McDonald, M. J. Ferguson, M. Cowie, Organometallics 2005, 24, 6194.
  456. S. Zhang, W. E. Piers, Organometallics 2001, 20, 2088.
  457. M. A. Alvarez, D. García-Vivo, M. E. García, M. E. Martínez, A. Ramos, M. A. Ruiz, Organometallics 2008, 27, 1973;
  458. M. Angeles Alvarez M. E. García, M. E. Martínez, A. Ramos, M. A. Ruiz, Organometallics 2009, 28, 6293; (c) M. A. Alvarez, M. E. García, M. E. Martínez, M. A. Ruiz, Organometallics 2010, 29, 904.

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