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Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH FRONT

Yes They Can: Small-molecule Activation with Stable Diaminocarbenes

Ulrich Siemeling
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Institute of Chemistry, University of Kassel, 34109 Kassel, Germany. Email: siemeling@uni-kassel.de

Australian Journal of Chemistry 64(8) 1109-1112 https://doi.org/10.1071/CH11244
Submitted: 15 June 2011  Accepted: 22 June 2011   Published: 19 August 2011

Abstract

Although small-molecule activation has long been the exclusive domain of transition metal chemistry, it has been increasingly realized that subvalent heavier main-group element compounds, too, are capable of activating H2, NH3, CO, etc. In a remarkable breakthrough, it was recently discovered that this is even possible with certain selected carbon(ii) compounds, viz. (alkyl)(amino)carbenes. However, N-heterocyclic carbenes and related diaminocarbenes, which represent the largest and most widely applied class of singlet carbenes, have been judged to be incapable of exhibiting similar reactivity. It now turns out that this is not quite true and that their reactivity needs to be reassessed.


References

[1]  Activation of Small Molecules: Organometallic and Bioinorganic Perspectives (Ed. W. B. Tolman) 2006 (Wiley-VCH: Weinheim).

[2]  J. Hartwig, Organotransition Metal Chemistry: from Bonding to Catalysis 2010 (University Science Books: Sausalito, CA).

[3]  G. H. Spikes, J. C. Fettinger, P. P. Power, J. Am. Chem. Soc. 2005, 127, 12232.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXotFSiu7s%3D&md5=80a2db2ed2dcfbebf34e9fc62ba0a4faCAS |

[4]  (a) For reviews, see: Asay  M., Jones  C., Driess  M., Chem. Rev. 2011 111, 354. 10.1021/CR100216Y
      (b) D. Scheschkewitz, Angew. Chem. Int. Ed. 2011, 50, 3118.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) S. Yao, Y. Xiong, M. Driess, Organometallics 2011, 30, 1748.
         | Crossref | GoogleScholarGoogle Scholar |
      (d) S. K. Mandal, H. W. Roesky, Chem. Commun. 2010, 46, 6016.
         | Crossref | GoogleScholarGoogle Scholar |

[5]  (a) D. Martin, M. Soleilhavoup, G. Bertrand, Chem. Sci. 2011, 2, 389.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXhvV2jur0%3D&md5=f095cdcd03662a0d8534c640b86cfb37CAS |
      (b) P. P. Power, Nature 2010, 463, 171.
         | Crossref | GoogleScholarGoogle Scholar |

[6]  A. Jana, C. Schulzke, H. W. Roesky, J. Am. Chem. Soc. 2009, 131, 4600.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXjtlentrs%3D&md5=3a423e6688a2c86c1bddf2f269a5b678CAS |

[7]  A. Jana, I. Objartel, H. W. Roesky, D. Stalke, Inorg. Chem. 2009, 48, 798.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXmsVCk&md5=4e0cf9fc85edcdea53f02d03e6170de0CAS |

[8]  Y. Peng, B. D. Ellis, X. Wang, P. P. Power, J. Am. Chem. Soc. 2008, 130, 12268.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXhtVeit7fI&md5=964b609a67c07a360636549455f72299CAS |

[9]  J. I. van der Vlugt, Chem. Soc. Rev. 2010, 39, 2302.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXmsFertrk%3D&md5=4dc477d607f2dd9e42b94edfe2685979CAS |

[10]  (a) G. D. Frey, V. Lavallo, B. Donnadieu, W. W. Schoeller, G. Bertrand, Science 2007, 316, 439.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXktlSkurw%3D&md5=8015fb121bb2c3c57af804264b970071CAS |
      (b) V. Lavallo, Y. Canac, B. Donnadieu, W. W. Schoeller, G. Bertrand, Angew. Chem. Int. Ed. 2006, 45, 3488.
         | Crossref | GoogleScholarGoogle Scholar |

[11]  (a) For a review, see: Nair  V., Vellalath  S., Babu  B. P., Chem. Soc. Rev. 2008 37, 2691. 10.1039/B719083M
      (b) D. Enders, O. Niemeier, A. Henseler, Chem. Rev. 2007, 107, 5606.
         | Crossref | GoogleScholarGoogle Scholar |

[12]  N-Heterocyclic Carbenes: from Laboratory Curiosities to Efficient Synthetic Tools (Ed. S. Díez-González) 2011 (Royal Society of Chemistry: Cambridge).
      N-Heterocyclic Carbenes in Transition Metal Catalysis (Ed. F. Glorius) 2007 (Springer: Berlin).
      N-Heterocyclic Carbenes in Synthesis (Ed. S. P. Nolan) 2006 (Wiley-VCH: Weinheim).

[13]  (a) T. W. Hudnall, J. P. Moerdyk, C. W. Bielawski, Chem. Commun. 2010, 4288.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXntVentL8%3D&md5=512bc7ba1d7d1f352b0055c65bfc4febCAS |
      (b) T. W. Hudnall, C. W. Bielawski, J. Am. Chem. Soc. 2009, 131, 16039.
         | Crossref | GoogleScholarGoogle Scholar |

[14]  V. César, N. Lugan, G. Lavigne, Eur. J. Inorg. Chem. 2010, 361.

[15]  (a) U. Siemeling, C. Färber, M. Leibold, C. Bruhn, P. Mücke, R. F. Winter, B. Sarkar, M. von Hopffgarten, G. Frenking, Eur. J. Inorg. Chem. 2009, 4607.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXhtlaltbjN&md5=1443cc754f35610d9030a1f6ee1e42efCAS |
      (b) U. Siemeling, C. Färber, C. Bruhn, Chem. Commun. 2009, 98.
         | Crossref | GoogleScholarGoogle Scholar |

[16]  D. M. Khramov, E. L. Rosen, V. M. Lynch, C. W. Bielawski, Angew. Chem. Int. Ed. 2008, 47, 2267.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXktV2rt7g%3D&md5=7638329536412133e678ea529c322a71CAS |

[17]  T. Dröge, F. Glorius, Angew. Chem. Int. Ed. 2010, 49, 6940.
         | Crossref | GoogleScholarGoogle Scholar |

[18]  U. Siemeling, C. Färber, C. Bruhn, M. Leibold, D. Selent, W. Baumann, M. von Hopffgarten, C. Goedecke, G. Frenking, Chem. Sci. 2010, 1, 697.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXhtl2nsLbF&md5=b4636153a0d99076dd1d062c35c94da5CAS |

[19]  C. Goedecke, M. Leibold, U. Siemeling, G. Frenking, J. Am. Chem. Soc. 2011, 133, 3557.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXitFWrurs%3D&md5=be3cb664cd95b6e5662b30a1513942a5CAS |

[20]  H. Staudinger, R. Endle, Ber. Dtsch. Chem. Ges. 1913, 46, 1437.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaC3sXhslKrtQ%3D%3D&md5=529dc2b3eb16144d9dd56fad02291733CAS |

[21]  H. Staudinger, Justus Liebigs Ann. Chem. 1907, 356, 51.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaD28Xms1Y%3D&md5=4183ec1dc66ea93b7d204eefe5d6e748CAS |

[22]  (a) For recent reviews, see: Paull  D. H., Weatherwax  A., Lectka  T., Tetrahedron 2009 65, 6771. 10.1016/J.TET.2009.05.079
      (b) F. P. Cossío, A. Arrieta, M. A. Sierra, Acc. Chem. Res. 2008, 41, 925.
         | Crossref | GoogleScholarGoogle Scholar |