Crystal structure of tetra[bis(diphenylphosphino)methane dioxide- O,O']dysprosium(III) tri(trifluoromethanesulfonate) — N,N'- dimethylformamide (1:2), [Dy(C25H22P2O2)4][CF3SO3]3 · 2C3H7NO

Bis(diphenylphosphino)methane Dioxide Complexes of Lanthanide Trichlorides: Synthesis, Structures and Spectroscopy

“…The high molecular weights make the microanalyses rather insensitive to the amount of water, but are generally consistent with a formulation [Ln(dppmO 2 ) 4 ]Cl 3 •nH 2 O (n = 6: Ce, Pr; n = 4: Nd, Sm, Eu, Gd), although the amount of lattice solvent probably varies with the sample and is unlikely to be stoichiometric. The presence of significant amounts of lattice solvent is common in lanthanide phosphine oxide systems [7][8][9][10], and although evident in X-ray crystal structures, it is often disordered and difficult to model. Obtaining good quality crystals of the complexes proved difficult, but crystals of the Ce, Sm and Gd salts were obtained from various organic solvents and the compositions are shown in Table 1.…”

“…Isolation of both the eight-and seven-coordinate complexes was possible only for Sm, Eu and Gd. However, one should note that the chloride counter ions also have some role, in that whilst in the LnCl 3 /dppmO 2 series tetrakis-dppmO 2 species did not form beyond Gd, the complex [Dy(dppmO 2 ) 4 ][CF 3 SO 3 ] 3 [9] has been isolated from dmf solution with triflate counter ions. The role that anions and solvents play in lanthanide chemistry is often overlooked [2], but can be critical in determining which complex is isolated from solution.…”

“…We reported bis(diphenylphosphino)methane dioxide (dppmO 2 ) formed square-antiprismatic Chemistry 2020, 2 948 cations [La(dppmO 2 ) 4 ] 3+ with Cl, I or [PF 6 ] counter ions, but lutetium gave only octahedral [Lu(dppmO 2 ) 2 X 2 ] + (X = Cl, I) and [Lu(dppmO 2 ) 2 Cl(H 2 O)] 2+ [8]. Other dppmO 2 complexes reported include several types with Ln(NO 3 ) 3 [4], [Dy(dppmO 2 ) 4 ][CF 3 SO 3 ] 3 [9], [Eu(dppmO 2 ) 4 ][ClO 4 ] 3 [10] [11]. Here, we report a systematic study of the systems LnCl 3 -dppmO 2 for all fourteen accessible lanthanides.…”

Crystal structure of bis(O,O'-tetraisopropylmethylenediphosphonate)- cerium(III) trinitrate, Ce(NO3)3[CH2P2O2(C3H7O)4]2

“…In our previous work, some lanthanide complexes with tetraisopropylmethylenediphosphonate (L) and bis(diphenylphosphino)methane dioxide (dppmo 2 )h ave been synthesized and structurally characterized [7][8][9][10]. When we attemp to synthesize Ce(NO 3 ) 2 Cl complex of tetraisopropylmethylenediphosphonate, an unexpected title compound was obtained as aproduct.…”