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.