CrossRef enabled

PAC Archives

Archive →

Pure Appl. Chem., 2003, Vol. 75, No. 9, pp. 1255-1261

http://dx.doi.org/10.1351/pac200375091255

Mechanism of the opening of the closo-NB11 clusters by bases

Peter Paetzold, Jens Müller, Franc Meyer and Petra Lomme

Institut für Anorganische Chemie, Technische Hochschule Aachen, D-52056 Aachen, Germany

Abstract: The icosahedral aza-closo-dodecaboranes RNB11H11(R = H, Me, Ph) are opened by neutral bases L or anionic bases Xto give the nido-species RNB11H11L or [RNB11H11X], respectively, with a nonplanar pentagonal aperture; the N atom and a BHB hydrogen bridge are situated at opposite sides of the aperture. The BL or the BX vertex is found in the aperture either adjacent to the hydrogen bridge (type 1; C1) or adjacent to nitrogen (type 2;C1) or off the aperture adjacent to nitrogen on a mirror plane (type 3;Cs). At any rate, the isomer of type 1 is the primary product, which may rearrange to yield an isomer of type 3 via an isomer of type 2. Working in deuteromethanol shows that the bridging H atom originates from the primarily attacked BH vertex. The process from RNB11H11 to its base adduct of type 3 includes the opening and the closure of skeletal BN bonds and the jumping of the extra-H atom from endo into bridging positions and vice versa, whereas the base does not alter its position. The application of the opening process to a series of aza-closo-dodecaboranes with non-hydrogen boron ligands confirms that only atoms of the ortho-belt of the starting material are involved in structural changes. The elementary steps from the closo -species to the three isomers are identified as a [3c, 1c] collocation and subsequent [3c, 2c] translocations in the picture of molecular orbitals localized over three or two centers or to one center (lone pair).