Ruthenium and rhodium nitrosyl complexes containing dichalcogenoimidodiphosphinate ligands

Abstract

Interaction of [Ru(NO)Cl 3(PPh 3) 2] with K[N(R 2PS) 2] in refluxing N, N-dimethylformamide afforded trans-[Ru(NO)Cl{N(R 2PS) 2} 2] (R = Ph ( 1), Pr i ( 2)). Reaction of [Ru(NO)Cl 3(PPh 3) 2] with K[N(Ph 2PSe) 2] led to formation of a mixture of trans-[Ru(NO)Cl{N(Ph 2PSe) 2} 2] ( 3) and trans-[Ru(NO)Cl{N(Ph 2PSe) 2}{Ph 2P(Se)NPPh 2}] ( 4). Reaction of Ru(NO)Cl 3 · xH 2O with K[N(Ph 2PO) 2] afforded cis-[Ru(NO)(Cl){N(Ph 2PO) 2} 2] ( 5). Treatment of [Rh(NO)Cl 2(PPh 3) 2] with K[N(R 2PQ) 2] gave Rh(NO){N(R 2PQ) 2} 2] (R = Ph, Q = S ( 6) or Se ( 7); R = Pr i , Q = S ( 8) or Se ( 9)). Protonation of 8 with HBF 4 led to formation of trans-[Rh(NO)Cl{HN(Pr i 2PS) 2} 2][BF 4] 2 ( 10). X-ray diffraction studies revealed that the nitrosyl ligands in 2 and 4 are linear, whereas that in 9 is bent with the Rh–N–O bond angle of 125.7(3)°.