Synthesis and Reactivity of a CAAC–Aminoborylene Adduct: A Hetero-Allene or an Organoboron Isoelectronic with Singlet Carbenes†
Fatme Dahcheh
Joint UCSD-CNRS Research Chemistry Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, CA 92093-0343 (USA)
Department of Chemistry, University of Toronto, 80 St. George St. Toronto, ON M5S 3H6 (Canada)
Search for more papers by this authorDr. David Martin
Joint UCSD-CNRS Research Chemistry Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, CA 92093-0343 (USA)
Search for more papers by this authorCorresponding Author
Prof. Dr. Douglas W. Stephan
Department of Chemistry, University of Toronto, 80 St. George St. Toronto, ON M5S 3H6 (Canada)
Douglas W. Stephan, Department of Chemistry, University of Toronto, 80 St. George St. Toronto, ON M5S 3H6 (Canada)
Guy Bertrand, Joint UCSD-CNRS Research Chemistry Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, CA 92093-0343 (USA)
Search for more papers by this authorCorresponding Author
Prof. Dr. Guy Bertrand
Joint UCSD-CNRS Research Chemistry Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, CA 92093-0343 (USA)
Douglas W. Stephan, Department of Chemistry, University of Toronto, 80 St. George St. Toronto, ON M5S 3H6 (Canada)
Guy Bertrand, Joint UCSD-CNRS Research Chemistry Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, CA 92093-0343 (USA)
Search for more papers by this authorFatme Dahcheh
Joint UCSD-CNRS Research Chemistry Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, CA 92093-0343 (USA)
Department of Chemistry, University of Toronto, 80 St. George St. Toronto, ON M5S 3H6 (Canada)
Search for more papers by this authorDr. David Martin
Joint UCSD-CNRS Research Chemistry Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, CA 92093-0343 (USA)
Search for more papers by this authorCorresponding Author
Prof. Dr. Douglas W. Stephan
Department of Chemistry, University of Toronto, 80 St. George St. Toronto, ON M5S 3H6 (Canada)
Douglas W. Stephan, Department of Chemistry, University of Toronto, 80 St. George St. Toronto, ON M5S 3H6 (Canada)
Guy Bertrand, Joint UCSD-CNRS Research Chemistry Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, CA 92093-0343 (USA)
Search for more papers by this authorCorresponding Author
Prof. Dr. Guy Bertrand
Joint UCSD-CNRS Research Chemistry Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, CA 92093-0343 (USA)
Douglas W. Stephan, Department of Chemistry, University of Toronto, 80 St. George St. Toronto, ON M5S 3H6 (Canada)
Guy Bertrand, Joint UCSD-CNRS Research Chemistry Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, CA 92093-0343 (USA)
Search for more papers by this authorG.B. is grateful to the NSF (CHE-1359809) and DOE (DE-FG02-13ER16370) for financial support of this work. D.W.S. is grateful for the support of the NSERC of Canada and the award of a Canada Research Chair. F.D. acknowledges exchange support from the University of Toronto. CAAC=cyclic (alkyl)(amino)carbene.
Graphical Abstract
Boron can do it! The first carbene that was stable at room temperature had a pseudo allenic structure, but owing to its high flexibility, it featured classical carbene reactivity. Similarly, a stable boron compound, isoelectronic with singlet carbenes, has an allenic structure, and is able to activate CO and H2.
Abstract
A one-electron reduction of a cyclic (alkyl)(amino)carbene (CAAC)–bis(trimethylsilyl)aminodichloroborane adduct leads to a stable aminoboryl radical. A second one-electron reduction gives rise to a CAAC–aminoborylene adduct, which features an allenic structure. However, in manner similar to that of stable electrophilic singlet carbenes, this compound activates small molecules, such as CO and H2.
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