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

• Published in: Inorganic chemistry communications 2011-10, Vol.14 (10), p.1665-1668
• Main Authors: Li, Duan-Xiu, Ren, Zhi-Gang, Wang, Hui-Fang, Lang, Jian-Ping
• Format: Article
• Language: English
• Subjects: Aminothiocarbamide; Crystal structure; In situ formation; N,N-bis(diphenylphosphanylmethyl)aminothiocarbamide; Silver(I)
• ISSN: 1387-7003; 1879-0259
• DOI: 10.1016/j.inoche.2011.07.002

Reaction of silver nitrate with N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylenediamine (dppeda) in the presence of aminothiocarbamide in CH 2Cl 2/MeOH afforded an unexpected and low-yield binuclear complex [Ag 2(dppatc) 2](NO 3) 2·2MeOH (dppatc = N,N-bis(diphenylphosphanylmethyl)aminothiocarbamide) ( 1). An X-ray analysis revealed that the [Ag 2(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 Ag P 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 AgNO 3 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 [Ag 2(dppatc) 2](NO 3) 2·2MeOH (dppatc = N,N-bis(diphenylphosphanylmethyl)aminothiocarbamide) ( 1) was generated from the in situ reaction of AgNO 3 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 AgNO 3 with dppatc produced 1 in high yields. [Display omitted] ► Reaction of AgNO 3 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 AgNO 3 with dppatc produced 1 in a relatively high yield.