Übergangsmetall-Komplexe mit Schwefelliganden, XXVII Synthese und Reaktivität der Nitrosyl-und Nitrido-Ruthenium-Komplexe mit 1,2-Benzoldithiolat-Liganden [Ru(NO)(S2C6H4) 2]- bzw. [Ru(N)(S2C6H4)2]- / Transition Metal Complexes with Sulfur Ligands, XXVII Synthesis and Reactivity of the Nitrosyl- and Nitrido-Ruthenium Complexes with 1,2-Benzenedithiolate Ligands [Ru(NO)(S2C6H4)2]- and [Ru(N)(S2C6H4)2]-, Respectively

Abstract

The reaction of [Ru(NO)2(PPh3)2], [RuCl(NO)2(PPh3)2]PF6 or [RuCl3(NO)(PPh3)2] with 1,2- benzenedithiolate(-2), C6H4S2 2-, leads to the 16e--complex [Ru(NO)(S2C6H4)2]-, which was isolated as the NBu4 + salt (1). The square pyramidal anion in [NBu4)[Ru(NO)(S2C6H4)2] coordinates PMe3 with rearrangement of the sulfur ligands to give the six-coordinate cis- [NBu4][Ru(NO)(PMe3)(S2ChH4)2] (3); the rearrangement of the C6H4S2 2--Iigands from trans to cis coordination is proved by 13C NMR spectroscopy. [Ru(NO)(S2C6H4)2]- is rapidly reduced even under mild conditions. Reaction of 1 with NaBH4 in MeOH leads to the reduction of NO to a nitrido ligand and the concomitant oxidation of (formal) Ru(III) to Ru(VI) yielding [NBu4][Ru(N)(S2C6H4)2] (2). This compound is also formed when the nitrosyl complex is reacted withSiMe3N3.[Ru(NO)2(PPh3)2] and [RuCl(NO)2(PPh3)2]PFare denitrosylated by dttd2- (dttd2- = 2,3,8,9-dibenzo-1,4,7,10-tetrathiadecane(-2)) to give [Ru(dttd)(PPh3)2]