Platinum(II) Mixed Ligand Complexes with Thiourea Derivatives, Dimethyl Sulphoxide and Chloride: Syntheses, Molecular Structures, and ESCA Data

Abstract

The platinum(II) mixed ligand complexes [PtCl(L 1-6 )-(dmso)] with six differently substituted thiourea derivatives HL, R 2 NC(S)NHC(O)RЈ (R ϭ Et, RЈ ϭ p-O 2 N-Ph: HL 1 ; R ϭ Ph, RЈ ϭ p-O 2 N-Ph: HL 2 ; R ϭ RЈ ϭ Ph: HL 3 ; R ϭ Et, RЈ ϭ o-Cl-Ph: HL 4 ; R 2 N ϭ EtOC(O)N(CH 2 CH 2 ) 2 N, RЈ ϭ Ph: HL 5 ) and Et 2 NC(S)Nϭ CNH-1-Naph (HL 6 ), as well as the bis(benzoylthioureato-κO,κS)platinum(II) complexes [Pt(L 1,2 ) 2 ] have been synthesized and characterized by elemental analysis, IR, FAB(ϩ)-MS, 1 H-NMR, 13 C-NMR, as well as X-ray structure analysis ([PtCl(L 1 )(dmso)] and [PtCl(L 3,4 )(dmso)]) and ESCA ([PtCl(L 1,2 )(dmso)] and [Pt(L 1,2 ) 2 ]). The mixed ligand complexes [PtCl(L)(dmso)] have a nearly square-planar coordination at the platinum atoms. After deprotonation, the thiourea derivatives coordinate bidentately via O and S, DMSO bonds monodentately to the Pt II atom via S atom Platin(II)-Gemischtliganden-Komplexe mit Thioharnstoffderivaten, Dimethylsulfoxid und Chlorid: Synthesen, Molekülstrukturen und ESCA-Daten Inhaltsübersicht. Es wurden die Platin(II)-Gemischtliganden-Komplexe [PtCl(L 1-6 )(dmso)] mit sechs unterschiedlich substituierten Thioharnstoffderivaten HL, R 2 NC(S)NHC(O)RЈ (R ϭ Et, RЈ ϭ p-O 2 N-Ph: HL 1 ; R ϭ Ph, RЈ ϭ p-O 2 N-Ph: HL 2 ; R ϭ RЈ ϭ Ph: HL 3 ; R ϭ Et, RЈ ϭ o-Cl-Ph: HL 4 ; R 2 N ϭ EtOC(O)N(CH 2 CH 2 ) 2 N, RЈ ϭ Ph: HL 5 ) und Et 2 NC(S)NϭCNH-1-Naph (HL 6 ), sowie die Bis(benzoylthioureato-κO,κS)-platin(II)-Komplexe [Pt(L 1,2 ) 2 ] dargestellt und mittels Elementaranalyse, IR, FAB(ϩ)-MS, 1 H-NMR, 13 C-NMR, sowie Röntgenkristallstrukturanalyse ([PtCl(L 1 )(dmso)] und [PtCl(L 3,4 )(dmso)]) und ESCA ([PtCl(L 1,2 )(dmso)] und [Pt(L 1,2 ) 2 ]) charakterisiert. Die Gemischtliganden-Komplexe [PtCl(L)(dmso)] weisen eine nahezu quadratisch-planare Koordination an den Platinatomen auf. Die Thioharnstoffderivate koordinieren nach Deprotonierung bidentat über O und S, DMSO bindet

Rhenium and Technetium Complexes with Pentadentate Thiocarbamoylbenzamidines: Steps toward Bioconjugation

“…It is partially overlapped with the strong absorption of the ν CN stretch at 1631 cm –1 . The 1 H NMR spectrum of H 3 L shows two well-separated signal sets of two ethyl groups due to the hindered rotation of the NEt 2 moiety around the C­(S)–NEt 2 bond. ,,, While a singlet at 3.99 ppm is assigned to the methylene protons of CH 2 CO, a doublet at 4.64 with J = 5.2 Hz is typical for the methylene protons of CH 2 NH. The chemical shifts of the aromatic protons belonging to the aminobenzylamine appear in the range from 6.8 to 7.3 ppm, which is at higher field as compared to those of the other phenyl group.…”

ReVO and ReVNPh complexes with pentadentate benzamidines – Synthesis, structural characterization and DFT evaluation of isomeric complexes

“…Very strong absorptions around 1720 cm -1 are assigned to ν C=O vibrations, which are well separated from the strong absorptions of the ν C=N stretches in the 1616 cm -1 region [21][22][23][24]. The 1 H NMR spectra of H 3 L are characterized by two singlets around 3.45 ppm and 4.00 ppm, which are assigned to the methylene protons of NCH 2 CO and PhCH 2 N, respectively.…”

An Acyclic Diaminocarbene Complex of Platinum Formed by Desulfurization of 1,3‐Bis(3‐methylpyridin‐2‐yl)thiourea

“…[50] There are several examples for reactions of Pt II complexes with thiourea itself and substituted thiourea ligands such as 2,2'-dipyridyl-thiourea where nitrogen and sulfur can serve as coordination sites for Pt II . [45,46,[51][52][53][54][55][56][57][58][59] During ongoing studies in our lab, the reaction of 1,3-bis(3methylpyridin-2-yl)thiourea 1 with [PtCl 2 (dmso) 2 ] in dichloromethane (Scheme 1) was found to give a very insoluble nonfluorescing Pt complex 2 which could not easily be purified.…”

“…There are several examples for reactions of Pt II complexes with thiourea itself and substituted thiourea ligands such as 2,2′‐dipyridyl‐thiourea where nitrogen and sulfur can serve as coordination sites for Pt II [45,46,51–59] …”