The NOE experiment is demonstrated here as a viable tool in the NMR analyses of substituted borane and heteroborane compounds. We demonstrate that the saturation of 1 H NMR signals assigned to a substituent ligand can give rise to enhancements of signals arising from B-H's within a borane cage. These enhancements, though small (ca. 1-2%), are clearly detectable and have been used to confirm assignments for the pseudocloso-complex [1,2-Ph 2 -3-{Cp*}-3,1,2-IrC 2 B 9 H 9 ] (Cp*=η 5 -C 5 Me 5 ), the mono-substituted closo-carbaborane 1-Ph-1,2-C 2 B 1 0 H 1 1 and the di-substituted closo-carbaborane 1-Ph-2-Me-1,2-C 2 B 1 0 H 1 0 . We compare the results of applying three alternative experimental NOE procedures to these problems, namely phase sensitive 2D NOESY, 1D truncated driven NOE and 1D DPFGSE-NOE. The differences between the quality and relevance of these procedures to the study of borane and heteroborane derivatives are discussed.