A series of trimethylamine-thioborane adducts, Me3N center dot BH2SR (R = tBu [2a], nBu [2b], iPr [2c], Ph [2d], C6F5 [2e]) have been prepared and characterized. Attempts to access secondary and primary amine adducts of thioboranes via amine-exchange reactions involving these species proved unsuccessful, with the thiolate moiety shown to be vulnerable to displacement by free amine. However, treatment of the arylthioboranes, [BH2-SPh](3) (9) and C6F5SBH2 center dot SMe2 (10) with Me2NH and iPr(2)NH successfully yielded the adducts Me2NH center dot BH2SR (R = Ph [11a], C6F5 [12a]) and iPr(2)NH center dot BH2SR (R = Ph [11b], C6F5 [12b]) in high yield. These adducts were also shown to be accessible via thermally induced hydrothiolation of the aminoboranes Me2N=BH2, derived from the cyclic dimer [Me2N-BH2](2) (13), and iPr(2)N=BH2 (14), respectively. Attempts to prepare the aliphatic thiolate substituted adducts R2NH center dot BH2SR' (R = Me, iPr; R' = tBu, nBu, iPr) via this method, however, proved unsuccessful, with the temperatures required to facilitate hydrothiolation also inducing thermal dehydrogenation of the amine-thioborane products to form aminothioboranes, R2N=BH(SR'). Thermal and catalytic dehydrogenation of the targeted amine-thioboranes, 11a/11b and 12a/12b were also investigated. Adducts 11b and 12b were cleanly dehydrogenated to yield iPr(2)N=BH(SPh) (22) and iPr(2)N=BH(SC6F5) (23), respectively, at 100 degrees C (18 h, toluene), with dehydrogenation also possible at 20 degrees C (42 h, toluene) with a 2 mol % loading of [Rh(mu-Cl)cod](2) in the case of the former species. Similar studies with adduct ha evidenced a competitive elimination of H-2 and HSPh upon thermolysis, and other complex reactivity under catalytic conditions, whereas the fluorinated analogue 12a was found to be resistant to dehydrogenation.