New bidentate and tridentate ligands that feature selenium donors, namely the bis- and tris(2-seleno-1-R-imidazolyl)hydroborato ligands [Bse^R] and [Tse^R], have been constructed via the reaction of MBH₄ (M = Na, K) with 1-R-imidazole-2-selone (R = Me, Mes).  These ligands have been used to prepare a variety of compounds of both the main group metals and transition metals, including Zn, Cd, Hg, Ga, In, Co, Ni and Re. Comparison of the IR spectroscopic data of [Tse^R]Re(CO)₃ with those of a variety of related LRe(CO)₃ complexes demonstrates that the [Tse^R] ligands are more strongly electron donating than Cp, Cp*, [Tp], [Tp^Me,Me] and [Tm^Mes] ligands.  Interestingly, the [Bse^Me] ligand may form compounds which are structurally different than the [Bm^Me] counterpart, as illustrated by the fact that {[Bse^Me]ZnI}₂ exists as a selenium bridged dimer, whereas [Bm^Me]ZnI is a monomer.