Platinum Acetate Blue: Synthesis and Characterization

Abstract

Platinum acetate blue (PAB) of the empirical formula Pt(OOCMe)2.5±0.25, a byproduct in the synthesis of crystalline platinum(II) acetate Pt4(OOCMe)8, is an X-ray amorphous substance containing platinum in the oxidation state between (II) and (III). Typical PAB samples were studied with X-ray diffraction, differential thermal analysis-thermogravimetric, extended X-ray absorption fine structure, scanning electron microscopy, transmission electron microscopy, magnetochemistry, and combined quantum chemical density functional theory-molecular mechanics modeling to reveal the main structural features of the PAB molecular building blocks. The applicability of PAB to the synthesis of platinum complexes was demonstrated by the preparation of the new homo- and heteronuclear complexes Pt(II)(dipy)(OOCMe)2 (1), Pt(II)(μ-OOCMe)4Co(II)(OH2) (2), and Pt(III)2(OOCMe)4(O3SPhMe)2 (3) with the use of PAB as starting material.

Bimetallic Platinum Group Complexes of a Macrocyclic Pyrazolate/NHC Hybrid Ligand

“…Elemental analysis supported the presence of only PF 6 – anions leading to the conclusion that no anion exchange occurred. For the synthesis of the Pt II congener, the acetate route was not feasible because Pt­(OAc) 2 is not commercially available and the reported synthetic procedures lack reproducibility . Instead, we used readily available PtCl 2 (cod) to prepare Pt 2 L­(PF 6 ) 2 in the deprotonation approach.…”

“…For the synthesis of the Pt II congener, the acetate route was not feasible because Pt(OAc) 2 is not commercially available and the reported synthetic procedures lack reproducibility. 43 Instead, we used readily available PtCl 2 (cod) to prepare Pt 2 L(PF 6 ) 2 in the deprotonation approach. The reaction of the Pt II salt with H 6 L(PF 6 ) 4 in the presence of NaOAc at 80 °C afforded the respective Pt II −NHC complex.…”

Paramagnetic Metal–Metal Bonded Heterometallic Complexes

“…"Platinum acetate blue", a material with empirical formula Pt(OAc) 2.5 , was found to be synthetically useful for the preparation of the Pt−Co heterobimetallic compound B10 bridged by acetate ligands. 104 Self-assembly can also be used with the sulfur-containing ligands tba or SAc in aqueous solution to afford selectively the Pt−M heterobimetallic aquo compounds B11 and B25−B28. Compounds with other axial ligands can be prepared via ligand exchange.…”

“…To support the two metals, research groups have focused on providing either a 3-fold symmetric or a 4-fold symmetric coordination environment. The groups of Lu and Thomas have both utilized 3-fold symmetric ligand scaffolds to support a variety of unique heterobimetallic species. − Some of these species have found success in catalytic transformations and small molecule activation, ,,,,, cross-coupling reactions, ,,, and C–H activation. , Detailed description of their reactivity is described elsewhere. ,, In addition to these 3-fold symmetric species, the groups of Vargaftik, Doerrer, Zamora, and Berry have synthesized heterobimetallic compounds supported by four ligands in a paddlewheel arrangement, affording structures with C 4 symmetry. − Remarkably, the compounds comprising this section display a wide range of magnetic behavior, sometimes counterintuitive and surprising.…”

On the Heterogeneous Nature of Cisplatin‐1‐Methyluracil Complexes: Coexistence of Different Aggregation Modes and Partial Loss of NH3 Ligands as Likely Explanation

“…This applies, for example, to the so‐called “Platinum Pyrimidine Blues”, which are obtained by the reaction of the diaqua species of the anticancer agent Cisplatin, cis‐ [Pt(NH 3 ) 2 Cl 2 ], with pyrimidine nucleobases or related cyclic amides [5] . It is also true for the classical “Platinblau” [6] and the “Platinum Acetate Blue” [7] , which represent amorphous materials and are formed side by side with well‐characterized, crystalline products, yet frequently coloring the latter. Over the years, while applying a large number of different ligands, essential features of some of these materials have been recognized, such as multi‐nuclearity, stacking of dinuclear building blocks, and mixed‐valency [8,9] .…”