Transition metal solids have been exposed to fluorine, chlorine trifluoride and/or oxygen at temperatures up to 800-degrees-C, and the volatile reaction products analyzed by mass spectrometry. Reported here are the results of the reactions of the metals (sometimes partially oxidized) technetium, rhenium, tantalum and tungsten. The following vapor species have been identified: TcF5, TcO3F, TcOF4, TcO2F3, TcO3Cl, TcOCl3, TCO2Cl(x) (x = 2 or 3), TcOF2Cl, TcOFCl2, ReF6, ReO3F, ReO2F3, ReOF4, WF6, WO2F2, WOF4, WO2Cl2, WF5Cl, TaF5, TaOF3, TaOCl3 and TaF(x)Cl5-x (x = 1-4). The conditions under which these species were formed and their relevance to conventional condensed phase chemistry are discussed.