Synthesis and characterization of 1,1′-ferrocenyldichalcogenolato complexes of palladium and platinum

A rare class of heterobimetallic complexes [M{Fe(η5-EC5H4)2}(L)] [M = Pt, Pd; E = Se, Te; L = dppe = 1,2-bis(diphenylphosphino)ethane, dppf = 1,2-bis(diphenylphosphino)ferrocene] (1–7) containing the 1,1′-ferrocenylditellurolato and -selenolato ligands were synthesized by the reaction of [MCl2(L)] with Li2[Fe(η5-EC5H4)2] in thf. All complexes were characterized by 31P, 77Se, 125Te, and 195Pt NMR spectroscopy, as appropriate. The crystal structures of [Pt{Fe(η5-TeC5H4)2}(dppe)]·C7H8 (2·C7H8), [Pd{Fe(η5-SeC5H4)2}(dppe)]·C7H8 (3·C7H8), [Pd{Fe(η5-SeC5H4)2}(dppe)]·C7H8 (4·C7H8), and [Pt{Fe(η5-SeC5H4)2}(dppf)] (5) were determined by single crystal X-ray crystallography. All complexes exhibited the same or related structural motif. The simulation of the NMR spectra of 1, 6, and 7, for which no crystals were obtained, showed that these complexes also have the same molecular structure. The complexes (1–4) containing the chelating dppe ligand were more stable that those (5–7) containing the dppf ligand. In fact, [Pd{Fe(η5-TeC5H4)2}(dppf)] could not be obtained by the reaction of [PdCl2(dppf)] with Li2[Fe(η5-TeC5H4)2]. A small crop of crystals of [Fe(η5-C5H4Se)2CH2] (8) were observed upon slow decomposition of [Pd{Fe(η5-SeC5H4)2}(dppe)] and [Pt{Fe(η5-SeC5H4)2}(dppf)] in CH2Cl2.

Graphical abstractA series of [M{Fe(η5-EC5H4)2}(L)] [M = Pt, Pd; E = Se, Te; L = dppe = 1,2-bis(diphenylphosphino)ethane, dppf = 1,2-bis(diphenylphosphino)ferrocene] complexes were prepared and characterized by X-ray crystallography and 31P, 77Se, 125Te, and 195Pt NMR spectroscopy, as appropriate.Figure optionsDownload full-size imageDownload as PowerPoint slide