Thiosemicarbazonates of Ruthenium(II): Crystal Structures of [Bis(triphenylphosphine)][bis(N‐phenyl‐pyridine‐2‐carbaldehyde Thiosemicarbazonato)]ruthenium(II) and [Bis(diphenylphosphino)butane][bis(salicylaldehyde Thiosemicarbazonato)]ruthenium(II)

Abstract

AbstractReaction of RuCl2(PPh3)3 with N‐Phenyl‐pyridine‐2‐carbaldehyde thiosemicarbazone (C5H4N–C2(H)=N3‐N2H–C1(=S)N1HC6H5, Hpytsc‐NPh) in presence of Et3N base led to loss of ‐N2H‐proton and yielded the complex [Ru(pytsc‐NPh)2(Ph3P)2] (1). Similar reactions of precursor RuCl2[(p‐tolyl)3P]3 with a series of thiosemicarbazone ligands, viz. pyridine‐2‐carbaldehyde thiosemicarbazone (Hpytsc), salicylaldehyde thiosemicarbazone (H2stsc), and benzaldehyde thiosemicarbazone (Hbtsc), have yielded the complexes, [Ru(pytsc)2{(p‐tolyl)3P}2] (2), [Ru(Hstsc)2{(p‐tolyl)3P}]2 (3), and [Ru(btsc)2{(p‐tolyl)3P}2] (4), respectively. The reactions of precursor Ru2Cl4(dppb)3 {dppb = Ph2P–(CH2)4–PPh2} with H2stsc, Hbtsc, furan‐2‐carbaldehyde thiosemicarbazone (Hftsc) and thiophene‐2‐carbaldehyde thiosemicarbazone (Httsc) have formed complexes of the composition, [Ru(Hstsc)2(dppb)] (5), [Ru(btsc)2(dppb)] (6), [Ru(ftsc)2(dppb)] (7), and [Ru(ttsc)2(dppb)] (8). The complexes have been characterized by analytical data, IR, NMR (1H, 31P) spectroscopy and X‐ray crystallography (1 and 5). The proton NMR confirmed loss of –N2H– proton in all the compounds, and 31P NMR spectra reveal the presence of equivalent phosphorus atoms in the complexes. In all the compounds, thiosemicarbazone ligands coordinate to the RuII atom via hydrazinic nitrogen (N2) and sulfur atoms. The arrangement around each metal atom is distorted octahedral with cis:cis:trans P, P:N, N:S, S dispositions of donor atoms.