Different thermal reactivity of a 1,2-thiaphospholo[a]phosphirane in free and metal carbonyl complexed form

The W(CO)5 and Fe(CO)4 complexes of the bicyclic phosphirane 3,5,6,6-tetraphenyl-1phospha-2(right arrow)thiabicyclo[3.1.0]hex-3-ene undergo a thermal 2-phenylphosphirane dihydrophosphaisoindole ring expansion, while the free phosphirane suffers both a [2 + 1] cycloreversion and a fragmentation yielding a butadienyl sulfide.