Due to their octahedral symmetry, otherwise not available for carbon based chemistry, hypervalent sulfur fluorides are very attractive as structural building blocks for functional organic materials. Direct fluorination offers a convenient access to multigram quantities of highly stable bis(4-nitrophenyl)tetrafluorosulfurane Guided by molecular modeling, a novel catalytic process was devised to isomerize the predominantly formed cis isomer to the pure trans isomer.