201415-07-8Relevant academic research and scientific papers
Tris(diphenylthiophosphinoyl) methanide as tripod ligand in rhodium(III), iridium(III) and ruthenium(II) complexes
Valderrama, Mauricio,Contreras, Raul,Arancibia, Veronica,Munoz, Patricio,Boys, Daphne,Lamata, M. Pilar,Viguri, Fernando,Carmona, Daniel,Lahoz, Fernando J.,Lopez, Jose A.,Oro, Luis A.
, p. 507 - 517 (2007/10/03)
Reaction of the complex [{(η5-C5Me5)RhCl2}2], in CH2Cl2 solution, with AgBF4 (1:2 molar ratio) and (SPPh2)3CH leads to the cationic compound [(η5-C5Me5)RhCl{η2-(SPPh2)2CH(SPPh2)-S,S′}]BF4 (1) which is deprotonated by thallium(I) pyrazolate affording [(η5-C5Me5)Rh{η3-(SPPh2)3C-S,S′,S″}]BF4 (2a). The iridium dimer [{(η5-C5Me5)IrCl2}2] reacts with silver salts and (SPPh2)3CH, in CH2Cl2 or Me2CO, under analogous conditions, affording mixtures of [(η5-C5Me5)IrCl{η2-(SPPh2)2CH(SPPh2)-S,S′}]+ and [(η5-C5Me5)Ir{η3-(SPPh2)3C-S,S′,S″}]A [A = BF-4 (3a), PF-6 (3b)]. Addition of Et3N to the mixture gives pure complexes 3. The ruthenium complexes [{(η6-arene)RuCl2}2] (arene = C6Me6, p-MeC6H4Pri) react with (SPPh2)3CH, in the presence of AgA (A = PF-6 or BF-4) or Na BPh4, in CH2Cl2 or Me2CO, yielding only the deprotonated complexes [(η6-arene)Ru{η3-(SPPh2)3C-S,S'′,S″}]A [arene = C6Me6, A = BF4; arene = p-MeC6H4Pri, A = BPh4 (4a), PF6 (4b)]. The crystal structures of 3a and 4a were established by X-ray crystallography. Compound 3a crystallizes in the orthorhombic space group Pna21, with lattice parameters a = 41.477(6), b = 10.6778(11), c = 20.162(3) A and Z = 8. Complex 4a crystallizes in a monoclinic lattice, space group P21/n, with a = 20.810(4), b = 12.555(3), c = 23.008(4) A, β = 95.82(2)° and Z = 4. Both cationic complexes exhibit analogous pseudo-octahedral molecular structures with the anionic (SPPh2)3C- ligand bonded via the three sulphur atoms in a tripodal, tridentate fashion. Each metal centre completes its coordination environment with a η5-C5Me5 (3a) or a η6-MeC6H4Pri group (4a). A quite interesting result concerns the non-planarity of the methanide carbon which display P-C-P angles in the range 112.6-114.4(5)° in 3a and 111.9-113.6(4)° in 4a. The redox chemistry of the complexes was investigated by cyclic voltammetry. The Rh(III) complexes are quasi-reversibly reduced to Rh(I) and the Ir(III) complex is irreversibly reduced to Ir(I) in acetonitrile solutions. The Ru(II) complex undergoes a quasi-reversible reduction to Ru(I) and a reversible oxidation to Ru(III).
