Crystal Structure of a Novel Polymer of Hexakis(.MU.-diethyl phosphato)(triethyl phosphate)dicerium(III), C30H75Ce2O28P7

Abstract

Recently, we reported the synthesis and crystal structure of [La(µ-DMP)2(µ3-NO3)(DMSO)]n, 1 [UO2(µ-DEP)4(DMSO)]n, 2 [UO2(µ-DMP)4(DMSO)]n, 3 and [Cu2(µ-DMP)4(DMSO]n, 4 (DMP = dimethyl phosphate and DMSO = dimethyl sulfoxide). In these complexes, DMP and DEP act as an O-atom donor ligand, forming coordination polymers in the solid state. Also, we reported the synthesis and crystal structures of [Ni(H2O)6](DMP)2 as an ionic complex. 5 In this complex, DMP is not bonded to the metal, and acts as a counter-ion. We now report on the synthesis and crystal structure of the title compound.Preparation: The title compound was obtained from a reaction between triethyl phosphate with CeCl3·7H2O in tetrahydroforan in a 4:1 molar ratio. Notably, the DEP ligand was obtained by eliminating one C2H5 molecule from the TEP ligand in the reaction mixture. Slow evaporation of this solution resulted an prismatic colorless crystals after two months.The X-ray data were collected on a diffractometer (Mo Kα radiation, graphite monochromator) at 120(2)K. The crystal data and experimental parameters are given in Table 1. As can be seen in Table 1, the highest peak, 4.838 eÅ -3 , is found close to the Ce atom. The non-hydrogen atoms were refined anisotropically, and all hydrogen atoms were located from sequent difference Fourier maps and refined with the riding model to final R indices of R1(0.0614) and WR2(0.1280).The X-ray structural analysis in Fig. 1 consists of a Ce2(µ-DEP)6(TEP) fragment and a repeation unit in this polymer. As is clear from an ORTEP view of the compound, Fig. 2, the repeation unit of this linear polymer consists of two 6 and 7-coordinated cerium atoms, which are linked together via six O-P-O bridges from phosphate esters. The seventh site of one of the cerium atoms is occupied by TEP as a monodentede ligand. Selected bond lengths and angles are given in The crystal structure of [Ce2(µ-DEP)6(TEP)]n, (DEP = diethyl phosphate), (TEP = triethyl phosphate) was determined by the X-ray diffraction method. This polymeric complex crystallizes in the monoclinic system, with space group P21/c, and the following unit-cell dimension: a = 19.517 (4)

Isomorphous rare-earth tris[bis(2,6-diisopropylphenyl) phosphate] complexes and their catalytic properties in 1,3-diene polymerization and in the inhibited oxidation of polydimethylsiloxane

“…Established structures of bi-and mononuclear complexes are particularly rare. The crystal structures of tris(dialkyl/diaryl phosphate) complexes of rare earths are mainly coordination polymers bearing dimethyl/ diethyl phosphate ligands [see the Cambridge Structural Database (CSD), Version 5.38 with updates, May 2017; Groom et al, 2016]: [Ln{(MeO) 2 PO 2 } 3 ] 1 [Ln = La (CSD refcode HEBDEX; Guang-Fu et al, 1994), Nd (LAHREU; Lumetta et al, 2016), Sm (JEVVOV; Li et al, 1989) and Eu (KIXGON;Li et al, 1991)], [La{(MeO) 2 PO 2 } 3 (H 2 O)] 1 (JIGVEA; Liu et al, 1990) and [Ln{(EtO) 2 PO 2 } 3 ] 1 {Ln = Nd [BOVREJ (Lebedev et al, 1982) and BOVREJ01 (Rafizadeh et al, 2009)], Ce [JOGJEU (Han et al, 1990) and KETWUC (Amani et al, 2006)] and Pr (JOGJIY; Han et al, 1990)}. The coordination polymer structures of the tris(dialkyl phosphate) complexes usually lead to poorer catalytic activity.…”

Tris(ethylenediamine-κ2N,N′)nickel(II) bis(dimethyl phosphate)

“…For related structures, see: Amani et al (2006); Jun & Zhang (2010); Rafizadeh & Amani (2006a,b, 2007; Rafizadeh, Amani & Aghayan (2006); Rafizadeh, Amani & Broushaky (2006); Rafizadeh, Hoseinzadeh & Amani (2006); Rafizadeh et al (2005Rafizadeh et al ( , 2009.…”

Dinuclear neodymium and lanthanum bis(2,6-diisopropylphenyl) phosphate complexes bearing a hydroxide ligand: catalytic activity of the Nd complex in 1,3-diene polymerization

“…For example, neodymium organophosphates and carboxylates could be applied successfully as precatalysts for 1,3-diene polymerization (Evans et al, 2001;Evans & Giarikos, 2004;Fischbach et al, 2006;Fischbach & Anwander, 2006;Friebe et al, 2006;Jang et al, 2000;Kwag, 2002 Previously described Nd-organophosphate precatalysts either did not have a definite composition but possessed high catalytic activity or had determined crystal structures (usually being coordination polymers) but exhibited rather low catalytic activity in diene polymerization. Some examples of rareearth tris(dialkyl phosphates) having coordination polymer structures are [Ln{(MeO) 2 PO 2 } 3 ] 1 {Ln = La [Cambridge Structural Database (CSD;Version 5.38 with updates, May 2017;Groom et al, 2016) refcode HEBDEX (Zeng et al, 1994)], Nd (LAHREU; Lumetta et al, 2016), Sm (JEVVOV; Li et al, 1989) and Eu (KIXGON;Li et al, 1991)}, [La{(MeO) 2 PO 2 } 3 (H 2 O)] 1 (JIGVEA; Liu et al, 1990) and [Ln{(EtO) 2 PO 2 } 3 ] 1 {Ln = Nd [BOVREJ (Lebedev et al, 1982) and BOVREJ01 (Rafizadeh et al, 2009)] and Ce [JOGJEU (Han et al, 1990) and KETWUC (Amani et al, 2006)]}. The coordination polymer structure of the tris(dialkyl phosphate) complexes usually leads to their having poorer catalytic activity.…”