Simple Preparations of Pd₆Cl₁₂, Pt₆Cl₁₂, and Q_n[Pt₂Cl_8+n], n = 1, 2 (Q = TBA⁺, PPN⁺) and Structural Characterization of [TBA][Pt₂Cl₉] and [PPN]₂[Pt₂Cl₁₀]·C₇H₈

Abstract

The hexanuclear Pd6Cl12, i.e., the crystal phase classified as beta-PdCl2, was obtained by reacting [TBA]2[Pd2Cl6] with AlCl3 (or FeCl3) in CH2Cl2. The action of AlCl3 on PtCl42-, followed by digestion of the resulting solid in 1,2-C2H4Cl2 (DCE), CHCl3, or benzene, produced Pt6Cl12.DCE, Pt6Cl12.CHCl3, or Pt6Cl12.C6H6, respectively. Treating [TBA]2[PtCl6] with a slight excess of AlCl3 afforded [TBA][Pt2Cl9], whose anion was established crystallographically to be constituted by two "PtCl6" octahedra sharing a face. Dehydration of H2PtCl6.nH2O with SOCl2 gave an amorphous compound closely analyzing as PtCl4, reactive with [Q]Cl in SOCl2 to yield [Q][Pt2Cl9] or [Q]2[Pt2Cl10], depending on the [Q]Cl/Pt molar ratio (Q=TBA+, PPN+). A single-crystal X-ray diffraction study has shown [PPN]2[Pt2Cl10].C7H8 to contain dinuclear anions formed by two edge-sharing PtCl6 octahedra.

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

“…It is also possible to prepare [PtBr 2 (PPh 3 )(NCMe)] using 1 equivalent of [PtBr 2 (NCMe) 2 ] and 1 equivalent of [PtBr 2 (PPh 3 ) 2 ]. [15a] The last compound is readily accessible by the synthetic sequence depicted in Equation and Equation and it involves: preliminary extraction of platinum into dichloromethane solution as [TBA] 2 [PtBr 4 ] (TBA = tetrabutylammonium; DCM = dichloromethane) followed by a reaction with PPh 3 (phosphine/Pt = 2 in mol) …”

Unprecedented pentanuclear mixed-valence Pt(II)-Pt(IV) complex anion in Q2[Pt5Cl20] salts (Q = TBA, PPN)

“…These reactions, supposed to be endoergonic and displaced to the left, can be favoured if Cl 2 is removed, for instance by reaction with the solvent (Eq 3, n = 1, 2). Actually, the reduction was not observed when the preparation was carried out in SOCl 2 [5], probably because this solvent is not a good halogen trap.…”

Clustering of palladium(II) chloride in acetonitrile solution investigated by electrospray mass spectrometry

“…However, notable differences for the various cluster sizes are apparent ( Fig. 5) with the largest amount of reduction for the hexanuclear clusters [15].…”