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The reaction of [Ru(NO) 2 (PPh 3 ) 2 ], [RuCl(NO) 2 (PPh 3 ) 2 ]PF 6  or [RuCl 3 (NO)(PPh 3 ) 2 ] with 1,2- benzenedithiolate(-2), C 6 H 4 S 2  2- , leads to the 16e - -complex [Ru(NO)(S 2 C 6 H 4 ) 2 ] - , which was isolated as the NBu 4  +  salt (1). The square pyramidal anion in [NBu 4 )[Ru(NO)(S 2 C 6 H 4 ) 2 ] coordinates PMe 3  with rearrangement of the sulfur ligands to give the six-coordinate cis- [NBu 4 ][Ru(NO)(PMe 3 )(S 2 ChH 4 ) 2 ] (3); the rearrangement of the C 6 H 4 S 2  2- -Iigands from trans to cis coordination is proved by  13 C NMR spectroscopy. [Ru(NO)(S 2 C 6 H 4 ) 2 ] -  is rapidly reduced even under mild conditions. Reaction of 1 with NaBH 4  in MeOH leads to the reduction of NO to a nitrido ligand and the concomitant oxidation of (formal) Ru(III) to Ru(VI) yielding [NBu 4 ][Ru(N)(S 2 C 6 H 4 ) 2 ] (2). This compound is also formed when the nitrosyl complex is reacted withSiMe 3 N 3 .  [Ru(NO) 2 (PPh 3 ) 2 ] and [RuCl(NO) 2 (PPh 3 ) 2 ]PF  are denitrosylated by dttd 2-  (dttd 2-  = 2,3,8,9-dibenzo-1,4,7,10-tetrathiadecane(-2)) to give [Ru(dttd)(PPh 3 ) 2 ]

zeitschrift für naturforschung b

Übergangsmetall-Komplexe mit Schwefelliganden, XXVII Synthese und Reaktivität der Nitrosyl-und Nitrido-Ruthenium-Komplexe mit 1,2-Benzoldithiolat-Liganden [Ru(NO)(S 2 C 6 H 4 )  2 ] -  bzw. [Ru(N)(S 2 C 6 H 4 ) 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)(S 2 C 6 H 4 ) 2 ] -  and [Ru(N)(S 2 C 6 H 4 ) 2 ] - , Respectively