The reaction of [Cp*TaCl4], 1 (Cp* = eta(5)-C5Me5), with [LiBH4 center dot THF] at -78 degrees C, followed by thermolysis in the presence of excess [BH3 center dot THF], results in the formation of the oxatantalaborane cluster [(Cp*Ta)(2)B4H10O], 2 in moderate yield. Compound 2 is a notable example of an oxatantalaborane cluster where oxygen is contiguously bound to both the metal and boron. Upon availability of 2, a room temperature reaction was performed with [Fe-2(CO)(9)], which led to the isolation of [(Cp*Ta)(2)B2H4O{H2Fe2(CO)(6)BH} ] 3. Compound 3 is an unusual heterometallic boride cluster in which the [Ta2Fe2] atoms define a butterfly framework with one boron atom lying in a semi-interstitial position. Likewise, the diselenamolybdaborane, [(Cp*Mo)(2)B4H4Se2], 4 was treated with an excess of [Fe-2(CO)(9)] to afford the heterometallic boride cluster [(Cp*MoSe)(2)Fe-6(CO)(13)B-2(BH)(2)], 5. The cluster core of 5 consists of a cubane [Mo2Se2Fe2B2] and a tricapped trigonal prism [Fe6B3] fused together with four atoms held in common between the two subclusters. In the tricapped trigonal prism subunit, one of the boron atoms is completely encapsulated and bonded to six iron and two boron atoms. Compounds 2, 3, and 5 have been characterized by mass spectrometry, IR, H-1, B-11, C-13 NMR spectroscopy, and the geometric structures were unequivocally established by crystallographic analysis. The density functional theory calculations yielded geometries that are in close agreement with the observed structures. Furthermore, the calculated B-11 NMR chemical shifts also support the structural characterization of the compounds. Natural bond order analysis and Wiberg bond indices are used to gain insight into the bonding patterns of the observed geometries of 2, 3, and 5.