Tetrakis(4‐amino‐1,2,4‐triazole)platinum(II) Salts: Syntheses, Crystal Structures, and Properties

Abstract

Transparent crystals comprising the nitrogen‐rich co­ordination unit [Pt(NH2trz)4]2+ were synthesized with counterions of various sizes but of the same charge (–1), yielding the compounds [Pt(NH2trz)4]Cl2·2H2O, [Pt(NH2trz)4](NO3)2 and [Pt(NH2trz)4](CF3SO3)2, with NH2trz designating 4‐amino‐1,2,4‐triazole. Single‐crystal X‐ray diffraction analysis showed that NH2trz coordinates with only the nitrogen atom in 1‐position in all compounds. The [Pt(NH2trz)4]2+ units are stacked such that the platinum atoms form linear arrays with Pt–Pt spacings mostly uncorrelated to anion size. The compound with the smallest anion (Cl–) has the smallest Pt–Pt spacing (4.72 Å) and shows a quasi‐one‐dimensional structure. Thermal decomposition of the compounds was observed around 200 °C. Electrical conductivity of [Pt(NH2trz)4]Cl2 and [Pt(NH2trz)4](SO3CF3)2 was investigated and found to be humidity‐dependent. Finally, [Pt(NH2trz)4]2+ ions obtained by dissolution of the chloride salt are shown to be useful for the synthesis of new compounds such as the Magnus' salt derivative [Pt(NH2trz)4][PtCl4].

A Cadmium Anionic 1-D Coordination Polymer {[Cd(H2O)6][Cd2(atr)2(μ2-btc)2(H2O)4] 2H2O}n within a 3-D Supramolecular Charge-Assisted Hydrogen-Bonded and π-Stacking Network

“…1,2,4-Triazol-4-yl derivatives match the coordination geometry of pyrazoles with their N1 and N2 donor atoms, and can form different secondary building units (SBUs). The amino-functionalized triazole ligand 4-amino-1,2,4-triazole (atr) can coordinate to metal atoms to build molecular complexes [9,10], polynuclear complexes [11,12], inorganic-organic coordination polymers [13][14][15][16] and different dimensional metal-organic networks of mixed ligands [17,18].…”

Trinuclear Complexes of Nickel(II) and 4‐Amino‐1,2,4‐triazole

“…[3] Two of these complexes were found to show a distinct dependence of the electric conductivity on the humidity, thus acting as humidity sensors. [3] Dinuclear and trinuclear complexes of the formula tances between the nickel atoms (3.72-3.73 Å) are too large to enable considerable Ni-Ni bonds. Remarkably, over longer periods hydrolyzed BF 4 -reacted with the glass vessel, in which the synthesis was conducted, to yield SiF 6 2-ions.…”

“…Remarkably, over longer periods hydrolyzed BF 4 -reacted with the glass vessel, in which the synthesis was conducted, to yield SiF 6 2-ions. In the resulting mixture, a BF 4 -/SiF 6 2-complex developed reproducibly, of the structure [Ni 3 (NH 2 trz) 6 (H 2 O) 6 ](BF 4 ) 4 (SiF 6 )·4H 2 O. Although both the BF 4 -and the BF 4 -/SiF 6 2-complexes are characterized by trinuclear units and exhibit similar Ni-N and Ni-O bond lengths as well as Ni-Ni distances, in the BF 4 -crystal there are two symmetrically inequivalent trinuclear units, while in the BF 4 -/SiF 6 2-crystal the two Ni-Ni subunits in a trinuclear unit differ from each other, in particular with respect to the angles between mean planes of the triazole molecules.…”

“…Accordingly, mononuclear or polynuclear NH 2 trz complexes with a number of metal ions have been identified by singlecrystal X-ray diffraction analysis. [3][4][5][6][7][8][9][10][11][12][13] Mononuclear compounds with NH 2 trz (N 1 binding mode) were obtained with platinum(II), resulting in complexes of the structure [Pt(NH 2 trz) 4 ]X 2 ·nH 2 O, (X = chloride (n = 2), nitrate (n = 0), or trifluoromethanesulfonate (n = 0)). [3] Two of these complexes were found to show a distinct dependence of the electric conductivity on the humidity, thus acting as humidity sensors.…”

“…[3][4][5][6][7][8][9][10][11][12][13] Mononuclear compounds with NH 2 trz (N 1 binding mode) were obtained with platinum(II), resulting in complexes of the structure [Pt(NH 2 trz) 4 ]X 2 ·nH 2 O, (X = chloride (n = 2), nitrate (n = 0), or trifluoromethanesulfonate (n = 0)). [3] Two of these complexes were found to show a distinct dependence of the electric conductivity on the humidity, thus acting as humidity sensors. [3] Dinuclear and trinuclear complexes of the formula tances between the nickel atoms (3.72-3.73 Å) are too large to enable considerable Ni-Ni bonds.…”