Versatile coordination of N-(diisopropoxyphosphoryl)-p-bromothiobenzamide towards Zn(II) and Cd(II)

Reaction of the potassium salt of N-(diisopropoxyphosphoryl)-p-bromothiobenzamide p-BrC6H4C(S)NHP(O)(OiPr)2 (HL) with Zn(II) and Cd(II) cations in aqueous EtOH leads to the three different complexes: [Zn(L-O,S)2] (1), [Cd(p-BrC6H4C(S)NH2-S)(L-O,S)2] (2) and [Cd(HL-O)2(L-O,S)2] (3). The structures of these compounds were investigated by single crystal X-ray diffraction analysis, IR, 1H and 31P NMR spectroscopy, MALDI TOF spectrometry, and microanalysis. The Zn(II) atom in complex 1 is in a distorted tetrahedral O2S2 environment formed by the CS sulfur atoms and the PO oxygen atoms of two deprotonated ligands. Complex 2 has a trigonal-bipyramidal coordination core, Cd(Oax)2(Seq)3, and two deprotonated ligand molecules L are coordinated in the axial positions through the oxygen atoms of the PO groups. The trigonal plane is formed by the sulfur atoms of two anionic ligands and one p-bromothiobenzamide. The Cd(II) cation in complex 3 has an octahedral environment, (Oax)2(Oeq)2(Seq)2, with two neutral ligand molecules coordinated in the axial positions through the oxygen atoms of the PO groups. The equatorial plane is formed by two anionic ligands in a typical 1,5-O,S-coordination mode. The corresponding neutral and deprotonated ligands are in a trans disposition.

Graphical abstractReaction of the potassium salt of N-(diisopropoxyphosphoryl)-p-bromothiobenzamide p-BrC6H4C(S)NHP(O)(OiPr)2 (HL) with Zn(II) and Cd(II) cations in aqueous EtOH leads to the three different complexes: [Zn(L-O,S)2] (1), [Cd(p-BrC6H4C(S)NH2-S)(L-O,S)2] (2) and [Cd(HL-O)2(L-O,S)2] (3). The structures of these compounds were investigated by single crystal X-ray diffraction analysis, IR, 1H and 31P NMR spectroscopy, MALDI TOF spectrometry, and microanalysis. The luminescence properties of the novel compounds and previously described complexes of thiobenzamide C6H5C(S)NHP(O)(OiPr)2 (HQ) with Zn(II) and Cd(II) cations: [Zn(Q-O,S)2] (4), [Cd2(Q-O,S)4] (5), [Cd(HQ-O)2(Q-O,S)2] (6), were also measured.Figure optionsDownload full-size imageDownload as PowerPoint slide