Übergangsmetallkomplexe mit Schwefelliganden, XVIII. Synthese und Reaktionen von [Ru(L)(PPh3)dttd]-Komplexen mit kleinen Stickstoffverbindungen L = NH3, N2H4, N2H3CH3, N2H3C6H5 sowie NO+ (dttd2- = 2,3;8,9-Dibenzo-1,4,7,10-tetrathiadecan (–2))/ Transition Metal Complexes with Sulfur Ligands, XVIII. Synthesis and Reactions of [Ru(L)(PPh3)dttd] Complexes with Small Nitrogen Compounds L = NH3, N2H4, N2H3CH3, N2H3C6H5 and NO+ (dttd2- = 2,3;8,9-Dibenzo-1,4,7,10-tetrathiadecane (–2))

Abstract

Abstract Reaktionen von [Ru(L)(PPh3)dttd]-Komplexen mit kleinen Stickstoffverbindungen L = NH3, N2H4, N2H3CH3, N2H3C6H5 sowie NO+ (dttd2-= 2,3;8,9-Dibenzo-l,4,7,10-tetrathiadecan (—2)) Transition Metal Complexes with Sulfur Ligands, XVIII* Synthesis and Reactions of [R u(L)(PPh3)dttd] Complexes with Small Nitrogen Com pounds L = N H 3, N2H 4, N2H 3C H 3, N2H 3C6H 5 and N O + (dttd2-= 2,3;8,9-D ibenzo-l,4,7,10-tetrathiadecane (—2)) D ieter Sellmann+ Ruthenium Sulfur C om plexes, N itrogen Ligands The com plex fragment [Ru(PPh3)dttd], (dttd2-= 2,3;8,9-dibenzo-l,4,7,10-tetrath iad ecane (— 2)), coordinates small nitrogen com pounds, which have only o-as well as a-jr-donor proper­ ties. The reactions o f [Ru(PPh3)2dttd] with L — N H 3, N 2H 4, N 2H 3C H 3 and N 2H 3C6H 5, respec­ tively, give the corresponding [R u(L)(PP h3)dttd] com plexes. O xidation o f the hydrazine com ­ plex [R u(N 2H 4)(PPh3)dttd] yields [a-N 2H 2{R u(PP h3)dttd }2], the first diazene com plex in which the unstable N 2H 2 is bound to a sulfur coordinated m etal center and stabilized by a 4 c —6 e Ru— N — N — Ru system , steric shielding as well as thiolate — S---H (n,h2)---N hydrogen bridges. The reactions of the ammonia and the hydrazine com plexes, respectively, with N O PF6 yield the nitrosyl com plex [R u (N O)(PP h3)dttd]PF6 as final product; in the case o f [R u(N 2H 4)(P P h3)dttd] the intermediate formation of an azido com plex is observed IR -spectroscopically.