178171-43-2Relevant academic research and scientific papers
Rhenium(V) Oxo Complexes of Novel N2S2 Dithiourea (DTU) Chelate Ligands: Synthesis and Structural Characterization
Lipowska, Malgorzata,Hayes, Brittany L.,Hansen, Lory,Taylor Jr., Andrew,Marzilli, Luigi G.
, p. 4227 - 4231 (2008/10/09)
The compounds RNHC(=S)NH(CH2)nNHC(=S)NHR were prepared in a search for new, relatively small N2S2 ligands. These dithiourea (DTU) ligands are the first chelates containing two potentially bidentate thiourea moieties. A one-step reaction of 1,3-diaminopropane (1) with aryl or alkyl isothiocyanates or of 1,2-diaminoethane (2) with phenyl isothiocyanate afforded the target ligands in excellent yields (95-98%). The ReV=0 complexes of RNHC(=S)NH(CH2)3NHC(=S)NHR ligands were obtained through ligand exchange reactions with Re(V) precursors. The chemistry required neither protection of the sulfur atoms for ligand synthesis nor deprotection prior to metal complexation. The structure of (1-phenyl-3-(3-phenylthioureido)propyl]thioureato)oxorhenium(V) (7a), determined by X-ray diffraction methods, revealed the expected pseudo-square-pyramidal geometry with an N2S2 basal and an apical oxo donor set. Both coordinated N's (Nc) were deprotonated. One uncoordinated N (Nu) was deprotonated, producing a neutral complex containing an unexpected new type of dianionic, four-membered N,S chelate. In the crystal, the Nu atoms, N(3)H and N(4), of one complex each formed an H-bond with N(4) and N(3)H, respectively, of a symmetry-related complex. The Nc-C-S bond angles (106.1(6) and 101.5(6)°) were severely distorted from the 120° expected for an sp2-hybridized C. However, these small bite angles and the large N-Re-N bond angle (86.1(3)°) allowed for the formation of two four-membered chelate rings with normal Re-N and Re-S bond distances. Attempts to prepare complexes with the PhNHC(=S)NH-(CH2)2(=S)NHPh ligand were unsuccessful. These results suggest that a central five-membered chelate ring is too small to accommodate bidentate coordination of both thiourea moieties. NMR studies in methanol established that the neutral complex with one uncoordinated N deprotonated was the favored form in neutral and basic solutions. However, under acidic conditions, a cationic form with both uncoordinated N's protonated was favored.
