Send to

Choose Destination
See comment in PubMed Commons below
J Am Chem Soc. 2008 Oct 29;130(43):14117-9. doi: 10.1021/ja806627s. Epub 2008 Oct 1.

Molecular tweezers for hydrogen: synthesis, characterization, and reactivity.

Author information

Department of Chemistry, University of Helsinki, P.O. Box 55, FIN-00014 Helsinki, Finland.


The first ansa-aminoborane N-TMPN-CH2C6H4B(C6F5)2 (where TMPNH is 2,2,6,6-tetramethylpiperidinyl) which is able to reversibly activate H2 through an intramolecular mechanism is synthesized. This new substance makes use of the concept of molecular tweezers where the active N and B centers are located close to each other so that one H2 molecule can fit in this void and be activated. Because of the fixed geometry of this ansa-ammonium-borate it forms a short N-H...H-B dihydrogen bond of 1.78 A as determined by X-ray analysis. Therefore, the bound hydrogen can be released above 100 degrees C. In addition, the short H...H contact and the N-H...H (154 degrees) and B-H...H (125 degrees) angles show that the dihydrogen interaction in N-TMPNH-CH2C6H4BH(C6F5)2 is partially covalent in nature. As a basis for discussing the mechanism, quantum chemical calculations are performed and it is found that the energy needed for splitting H2 can arise from the Coulomb attraction between the resulting ionic fragments, or "Coulomb pays for Heitler-London". The air- and moisture-stable N-TMPNH-CH2C6H4BH(C6F5)2 is employed in the catalytic reduction of nonsterically demanding imines and enamines under mild conditions (110 degrees C and 2 atm of H2) to give the corresponding amines in high yields.

PubMed Commons home

PubMed Commons

How to join PubMed Commons

    Supplemental Content

    Full text links

    Icon for American Chemical Society
    Loading ...
    Support Center