Schwefel(IV)1‐Verbindungen als Liganden, 19. Kationische Ruthenium‐Sulfen‐Komplexe: Synthese und Reaktionen. Kristallstrukturanalyse von [Cp*(Me3P)2Ru(CH2SO2)]PF6

Sulfur(IV) Compounds as Ligands, 19[1]. – Cationic Ruthenium‐Sulfene Complexes: Synthesis and Reactions. Crystal Structure Analysis of [Cp*(Me3P)2Ru(CH2SO2)]PF6 Methylene addition to coordinated sulfur dioxide yields the novel η2(C, S) sulfene complexes [Cp(dppm)Ru(CHRSO2)]PF6 (RH:3, Me: 4) and [Cp*(Me3P)2Ru(CH2SO2)]PF6 (5). An X‐ray structure determination of 5 reveals a relatively short C – S bond (167.5 pm). The sulfene complexes are powerful carbon electrophiles as shown by the rapid addition of halides, pseudohalides, amines, including „nonnucleophiles”︁ such as ethyldiisopropylamine and DBU, and phosphanes to 3. The regioselectivity of the reaction of 3 with enamines is opposite to that of free sulfene, i.e. coordination of the sulfene to ruthenium effects umpolung.