A series of complexes of the phosphorus-based TTF ligand o-P2 with the metal ions FeII, CoII, NiII, PdII, PtII, and AgI

Abstract

Reactions of 3,4-dimethyl-3',4'-bis(diphenylphosphino)tetrathiafulvalene, o-P2, with [BF(4)](-) salts of Fe(ii), Co(ii), Ni(II), Pd(II), and Pt(II) yield complexes of general formula [M(o-P2)(2)][BF(4)](2). Similar reactions between o-P2 and AgSbF(6) or AgPF(6) produced the salts [Ag(o-P2)(2)][X] where X = [SbF(6)](-) or [PF(6)](-). The resulting compounds were fully characterized by (1)H and (31)P{(1)H} NMR, infrared and electronic absorption spectroscopies, cyclic voltammetry, FAB-MS and single-crystal X-ray diffraction. The paramagnetic Co(II) compound exhibits an S = 3/2 state with large spin-orbit coupling contribution at higher temperatures and an effective S' = 1/2 state below 20 K. Electrochemical studies of the compounds indicate that the two functionalized TTF ligands are not in electronic communication and that they essentially behave as isolated redox centers.

Tetrathiafulvalene-based group XV ligands: Synthesis, coordination chemistry and radical cation salts

“…Later on [108], a single crystal X-ray study confirmed that the compound Fe3 contains two bis(phosphines) trans coordinated in the equatorial plane to the metallic center located on an inversion center, while the axial positions are occupied by two acetonitrile molecules (Fig. 15).…”

“…Cu(I) and Ag(I) complexes with the chelating diphosphine 104 have been reported as homoleptic bis(diphosphine) complexes [(104) 2 Cu] + and [(104) 2 Ag] + [108]. As shown in Fig.…”

“…Although the Co II complex Co8 (Scheme 50) containing two TTFphosphines 104 was mentioned already in 1998 [107], its solid state structure and full characterization were only recently reported [108].…”

“…Homoleptic complexes Ni7, Pd3, Pt3 (Scheme 54) incorporating only the 104 ligand were also obtained by Dunbar starting from the "naked" [108]. The three Ni7, Pd3 and Pt3 complexes, isolated as toluene solvate, are isomorphous (Fig.…”

“…A view of the tetrahedral Ag + complex with 104[108].Scheme 62. Gold (I) complexes of the tetraphosphine 103.…”