One cationic dinuclear silver(I) complex of dppatc formed in situ by replacing ethylenediamine units of dppeda through aminothiocarbamide

Reaction of silver nitrate with N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylenediamine (dppeda) in the presence of aminothiocarbamide in CH2Cl2/MeOH afforded an unexpected and low-yield binuclear complex [Ag2(dppatc)2](NO3)2·2MeOH (dppatc = N,N-bis(diphenylphosphanylmethyl)aminothiocarbamide) (1). An X-ray analysis revealed that the [Ag2(dppatc)2]2+ dication of 1 contains a centrosymmetric double half-open cage structure in which two Ag centers are bridged by a pair of the heteroscopionate dppatc ligands via four Ag-μ-S and four AgP bonds. The in situ-formed dppatc ligand in 1 could be readily generated by one-pot and high-yield reaction of diphenylphosphine with formaldehyde and aminothiocarbamide. Further reaction of AgNO3 with dppatc could produce 1 in a relatively high yield. The results provided an efficient route to the synthesis of dppatc and also an interesting insight into its coordination chemistry.

Complex [Ag2(dppatc)2](NO3)2·2MeOH (dppatc = N,N-bis(diphenylphosphanylmethyl)aminothiocarbamide) (1) was generated from the in situ reaction of AgNO3 with N,N,N',N'-tetra(diphenylphosphanylmethyl)ethylenediamine and aminothiocarbamide. The dppatc ligand could be readily formed by reaction of diphenylphosphine with formaldehyde and aminothiocarbamide while reaction of AgNO3 with dppatc produced 1 in high yields.Figure optionsDownload as PowerPoint slideHighlights
► Reaction of AgNO3 with dppeda and aminothiocarbamide gave complex 1 in a low yield.
► The dppatc ligand could be readily generated by the reaction of diphenylphosphine with formaldehyde and aminothiocarbamide.
► Reactions of AgNO3 with dppatc produced 1 in a relatively high yield.