The oxide fluoride chemistry of bromine, selenium and suplhur

The transition metal carbonyls [Re2(CO)10], [Mn2(CO)10] and [Ru(CO)3(PPh3)2], and elemental iodine have been reacted with Xe(OSeF5)2. The products have been fully characterised by a combination of mass spectrometry, infrared spectroscopy 19F, 13C and 31P{lcub}1H{rcub} (where appropriate) NMR spectroscopies. Further characterisation of the novel compounds Xe(OSeF5)2, [Re(CO)5(OSeF5)] and [Mn(CO)5(OSeF5)] by EXAFS spectroscopy is reported.;An extensive review of the halogen oxide fluorides has been carried out and attempts were made to synthesise a range of fluorides and oxide fluorides of bromine. The bromine fluorides [BrF2][AsF6], [BrF4][Sb2F11], K[BrF4] and Cs[BrF6] were successfully characterised using EXAFS spectroscopy. The compound Cs[BrOF4] has been synthesised and the application of EXAFS spectroscopy has yielded internal bond parameters.;The area of fluorosulphate chemistry has been reviewed and reactions have been carried out between the superacid HSO3F and a range of transition metal carbonyl complexes and Ti, Hf and Zr derivatives. The complexes produced were characterised using mass spectrometry, infrared spectroscopy and 1H, 13C, 13C{lcub}1H{rcub} and 19F NMR spectroscopies. The protonation of the carbonyl clusters [Ir4(CO)12], [Os3(CO)12] and [Ru3(CO)12] by HSO3F was investigated. The systems are found to be the same as those previously observed for the superacid AHF.