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)

Reaction of RuCl 2 (PPh 3 ) 3 with N‐Phenyl‐pyridine‐2‐carbaldehyde thiosemicarbazone (C 5 H 4 N–C 2 (H)=N 3 ‐N 2 H–C 1 (=S)N 1 HC 6 H 5 , Hpytsc‐NPh) in presence of Et 3 N base led to loss of ‐N 2 H‐proton and yielded the complex [Ru(pytsc‐NPh) 2 (Ph 3 P) 2 ] ( 1 ). Similar reactions of precursor RuCl 2 [( p ‐tolyl) 3 P] 3 with a series of thiosemicarbazone ligands, viz. pyridine‐2‐carbaldehyde thiosemicarbazone (Hpytsc), salicylaldehyde thiosemicarbazone (H 2 stsc), and benzaldehyde thiosemicarbazone (Hbtsc), have yielded the complexes, [Ru(pytsc) 2 {( p ‐tolyl) 3 P} 2 ] ( 2 ), [Ru(Hstsc) 2 {( p ‐tolyl) 3 P}] 2 ( 3 ), and [Ru(btsc) 2 {( p ‐tolyl) 3 P} 2 ] ( 4 ), respectively. The reactions of precursor Ru 2 Cl 4 (dppb) 3 {dppb = Ph 2 P–(CH 2 ) 4 –PPh 2 } with H 2 stsc, 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 ( 1 H, 31 P) spectroscopy and X‐ray crystallography ( 1 and 5 ). The proton NMR confirmed loss of –N 2 H– proton in all the compounds, and 31 P NMR spectra reveal the presence of equivalent phosphorus atoms in the complexes. In all the compounds, thiosemicarbazone ligands coordinate to the Ru II atom via hydrazinic nitrogen (N 2 ) 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.