Large-bite diboranes for the (1,2) complexation of hydrazine and cyanide. Academic Article uri icon


  • As part of our interest in the chemistry of polydentate Lewis acids as hosts for diatomic molecules, we have investigated the synthesis and coordination chemistry of bidentate boranes that feature a large boron-boron separation. In this paper, we describe the synthesis of a new example of such a diborane, namely 1,8-bis(dimesitylboryl)triptycene (2) and compare its properties to those of the recently reported 1,8-bis(dimesitylboryl)biphenylene (1). These comparative studies reveal that these two diboranes feature some important differences. As indicated by cyclic voltammetry, 1 is more electron deficient than 2; it also adopts a more compact and rigid structure with a boron-boron separation (4.566(5) ) shorter by 1 than that in 2 (5.559(4) ). These differences appear to dictate the coordination behaviour of these two compounds. While 2 remains inert toward hydrazine, we observed that 1 forms a very stable (1,2) hydrazine complex which can also be obtained by phase transfer upon layering a solution of 1 with a dilute aqueous hydrazine solution. The stability of this complex is further reflected by its lack of reaction with benzaldehyde at room temperature. We have also investigated the behaviour of 1 and 2 toward anions. In MeOH/CHCl3 (1/1 vol) both compounds selectively bind cyanide to form the corresponding (1,2) chelate complexes with a B-C[triple bond, length as m-dash]N-B bridge at their cores. Competition experiments in protic media show that the anionic cyanide complex formed by 1 is the most stable, with no evidence of decomplexation even in the presence of (C6F5)3B.

published proceedings

  • Chem Sci

author list (cited authors)

  • Chen, C., & Gabba, F. P.

publication date

  • January 1, 2018 11:11 AM