Protodemetallation reactions of some diphenylthallium(III) compounds with dicyclohexyldithiophosphinic acid. Crystal and molecular structures of [TlPh2{S2P(C6H11)2}], [TlPh{S2P(C6H11)2}2] and [Tl{S2P(C6H11)2}3]·CHCl3

Abstract

The treatment of diphenylthallium(III) compounds TlPh₂X [X = Br, OH or S₂P(C₆H₁₁)₂] with dicyclohexyldithiophosphinic acid, HS(S)P(C₆H₁₁)₂, led to ‘protodemetallation’i.e. loss of one or more phenyl groups from thallium, with formation of benzene and formation of [TlPh{S₂P(C₆H₁₁)₂}₂] and [Tl{S₂P(C₆H₁₁)₂}₃]·CHCl₃. The crystal structures of these compounds and that of [TlPh₂{S₂P(C₆H₁₁)₂}] were solved by X-ray diffraction, which indicated that they all crystallize in the triclinic space group P1 with Z= 2. For [TlPh₂{S₂P(C₆H₁₁)₂}]a= 10.141(1), b= 10.315(2) and c= 11.913(2)Å, α= 94.46(1), β= 101.45(1) and γ= 91.01(1)°; the thallium atom is co-ordinated to one carbon atom of each phenyl and to both sulfur atoms of a dicyclohexyldithiophosphinate ligand [S₂P(C₆H₁₁)₂], and weakly interacts with two neighbouring ligands. For [TlPh{S₂P(C₆H₁₁)₂}₂]a= 9.442(1), b= 10.809(2) and c= 18.256(2)Å, α= 80.41(1), β= 86.95(1) and γ= 72.52(1)°; the thallium atom is co-ordinated to a phenyl carbon atom and to both sulfur atoms of each anisobidentate S₂P(C₆H₁₁)₂ ligand. For [Tl{S₂P(C₆H₁₁)₂}₃](which incorporates a chloroform solvent molecule)a= 15.539(1), b= 16.23(3) and c= 10.556(1)Å, α= 103.13(1), β= 91.71(1) and γ= 111.56(2)°; the thallium atom is co-ordinated to three pairs of sulfur atoms from two very anisobidentate ligands and one practically isobidentate dithiophosphinate. The IR, Raman, and ¹H, ¹³C, ³¹P and ²⁰⁵Tl NMR spectra of the compounds have also been recorded and analysed.