Pyrolysis of an in-situ generated intermediate, produced in the reaction of [CpMoCl4], 1, (Cp= η5-C5Me5) with [LiBH4·THF], with an excess of difuryl ditelluride in toluene at 90 °C yielded syn and anti isomers of [CpMo(O)(μ-Te)] 2 (2, 3) and [Cp2Mo2O2(μ-O)(μ- Te)] (4, 5). In a similar fashion, dibenzyl diselenide yielded syn and anti isomers of [CpMo(O)(μ-Se)]2 (6, 7), along with the known nido-[(CpMo)2B4H8Se2]. Note that in parallel with 2-7, [(CpMo)2B5H9] was isolated as the major product in both cases. Compounds 2-7 have been isolated in modest yield as orange to brown crystalline solids. All the new compounds have been characterized in solution by mass, IR, 1H, 13C, 77Se and 125Te NMR spectroscopy, and the structural types were unequivocally established by crystallographic analysis of 2-4 and 7. © 2011 Elsevier Ltd. All rights reserved.