The intermolecular base-stabilised haloboranes Ph3P.BPhCl 2, Ph3P.BCl3, 4-Pic.BCl3, and 4-Pic.BPhCl 2 represent useful examples of haloborane complexes containing PPh 3 and 4-picoline donors from which salt elimination chemistry might be used to make M-B bonds. The structures of Ph3P.BPhCl 2 and 4-Pic.BCl3 have been determined by single crystal X-ray diffraction and the structure of THF-BCl3 has been obtained for comparative purposes. The course of salt elimination chemistry with these boranes is highly dependent on the nature of the coordinated base; a bridging borylene complex [(C5H5)Fe(CO)2] 2 BPh has been synthesised and spectroscopically characterized using Ph3P.BPhCl2 as the boron-containing precursor.