A Sound Sequence to Triphenylphosphino Dibromoplatinum(II) Complexes – Solvothermal Preparation of trans‐[PtBr(µ‐Br)(PPh₃)]₂

Abstract

A sound synthetic procedure for the preparation of trans‐[PtBr(µ‐Br)(PPh3)]2 is described. The species was fully characterized and used to obtain [PtBr2(PPh3)(L)] complexes (L = DMSO, p‐toluidine, pyridine) by a bridge‐splitting reaction. All products were fully characterized by NMR spectroscopy, together with cis‐[PtBr2(PPh3)(NCCH3)], obtained as an intermediate in the synthesis of the dinuclear precursor. Cis‐[PtBr2(PPh3)(NCCH3)] was also studied by X‐ray diffraction.

Dibromo–Isonitrile and N-acyclic Carbene Complexes of Platinum(II): Synthesis and Reactivity

“…The preparation of isonitrile derivatives [PtBr 2 (PPh 3 )(CNR)] was carried out according to the reaction depicted in Scheme 1. The dinuclear brominated precursor was prepared according to a convenient reported procedure, starting from the easily available [PtCl 2 (NCMe) 2 ] [45] (see Supplementary Material for the synthesis), while the chosen isonitrile ligands were commercially available.…”

Dibromo- and Dichlorotriphenylphosphino N-Acyclic Carbene Complexes of Platinum(II)—Synthesis and Cytotoxicity

“…The synthesis of the title compounds was carried out according to known procedures [34,35], in two steps (Scheme 1) starting from [Pt(µ-X)X(PPh 3 )] [50]. Briefly, the suitable dinuclear precursor was reacted with cyclohexyl isocyanide, affording in all cases a single product, to which a cis geometry was assigned, in strict analogy with similar compounds [34,35].…”

“…Dinuclear precursors trans-[Pt(µ-X)X(PPh 3 )] 2 (X = Cl, Br) were prepared according to described procedures. [50] Samples of 5-8 were prepared according to the described procedures [35]. Cyclohexyl isocyanide was purchased from ™Merck and used without further purification.…”

“…In a Schlenk tube equipped with a magnetic stirrer a cooled (0 • C) suspension of trans-[Pt(µ-X)X(PPh 3 )] 2 [50] (0.200-0.500 g) in 1,2-DCE (10-15 mL) was treated, under stirring, with a solution of cyclohexyl isocyanide in the same solvent ([c-HexNC]/[Pt] = 2.0 molar ratio). The mixture was warmed (25 • C) and a clear, yellow solution was obtained (2 h).…”

“…The potential alteration of the complexes' nature and/or of their activity in DMSO and DMSO/water solutions [53,54], makes a stability check necessary each time DMSO is used. In the case of triphenylphosphine complexes 1-4, the stability in DMSO and DMSO/H 2 O mixtures can be conveniently checked by 31 P NMR spectroscopy since the complexes originating from the substitution of isonitrile or NAC ligands by DMSO (cis-[PtX 2 (PPh 3 )(DMSO)], X = Cl, Br) are known [50]. Complex 4 was chosen as representative of the prepared complexes and was used to carry out the stability tests.…”