Synthesis and Crystal Structure Investigations of Trivalent Rare Earth (Y³⁺, Nd³⁺, Er³⁺) Thienyl‐Substituted Methoxides

Abstract

The synthesis and structural characterization of rare earth alkoxides with thiophene-based substituents are presented. ) and the structurally characterized tertiary alcohols HO-C(C 4 H 3 S) 3 (1) or HO-C(C 8 H 5 S 2 ) 3 (2). The metal alkoxide derivatives of these thiophene-substituted alcohols have been isolated as air-sensitive base adducts, their molecular structures being investigated by single-crystal X-ray crystallography. The coordination spheres around the metal centres are

Syntheses, Crystal Structures, and Physico‐Chemical Studies of Sodium and Potassium Alcoholates Bearing Thienyl Substituents and their Derived Luminescent Samarium(III) Alkoxides

“…The Sm–O(thf) distances are longer with 2.594(3) Å ( 16 ) and 2.552(5) Å ( 17 ) and are in the range of those observed for Sm(O‐2,6‐ i Pr 2 C 6 H 3 ) 3 (thf) 3 [2.542(2) Å] 19. These distances are also in accordance with those found for the compound {Nd[OC(C 4 H 3 S) 3 ] 3 (thf) 3 } · thf 5.…”

“…These angle values are comparable with those found for Sm(O‐2,6‐ i Pr 2 C 6 H 3 ) 3 (thf) 3 [102.29(6)° and 79.33(6)°, respectively] 19 or Sm(O‐2,4,6‐Me 3 C 6 H 2 ) 3 (thf) 3 [103.4(1) and 77.5(1)°, respectively] 20. The Sm–O–C(C 4 H 3 S) 3 angles of 170.5(3)° and Sm–O–C(C 16 H 13 S) angles of 173.3(5)° are also similar to those in {Nd[OC(C 4 H 3 S) 3 ] 3 (thf) 3 } · thf [169.9(1)°] 5 and in Sm(O‐2,4,6‐Me 3 C 6 H 2 ) 3 (thf) 3 [170.0(3)°] 20. TheSm–OC(C 4 H 3 S) 3 and Sm–OC(C 16 H 13 S) distances of 2.156(3) and 2.160(4) Å are comparable to those in Sm(O‐2,4,6‐Me 3 C 6 H 2 ) 3 (thf) 3 [2.160(0) Å] 20, Sm(O‐2,6‐ i Pr 2 C 6 H 3 ) 3 (thf) 3 [2.158(2) Å] 19 and [Sm(OC 6 H 2 t Bu 2 ‐2,6‐Me‐4) 3 (thf)] · thf [2.152(7) Å] 27.…”

“…Additional thf molecules are filling the crystal lattice with no interaction with the molecules (Figure 6). The overall structures of 16 and 17 are similar to that in {Nd[OC(C 4 H 3 S) 3 ] 3 (thf) 3 } · thf 5, Sm(O‐2,4,6‐Me 3 C 6 H 2 )(thf) 3 20 or Sm(O‐2,6‐ i Pr 2 C 6 H 3 ) 3 (thf) 3 19. The arrangement around the samarium atoms is distorted octahedral, as evidence the (C 4 H 3 S) 3 CO–Sm–OC(C 4 H 3 S) 3 [101.1(1)°] or (C 16 H 13 S)OC–Sm–OC(C 16 H 13 S) [102.3(2)°] and the O(thf)–Sm–O(thf) angles [73.7(1)° for 16 or 76.9(2)° for 17 ].…”

Tris(tetrahydrofuran-κO)tris[tris(thiophen-2-yl)methanolato-κO]terbium(III) tetrahydrofuran monosolvate

“…It is surrounded by three tris(2-thienyl)methoxido ligands and by three tetrahydrofurane molecules in a facial arrangement. This facial coordination geometry around the metal is similar to those described in our previous paper (Veith et al, 2008;Veith, Belot, Huch, Cui et al, 2010;. The aditional THF molecule also present in the crystal lattice has no interaction with the molecule.…”

“…For the preparation of some other lanthanide alkoxides containing thienyl substituents, see: Veith et al (2008) ;Veith, Belot, Huch, Cui et al (2010). For lanthanide alkoxides, see: Barnhart et al (1993); Evans et al (1997Evans et al ( , 1999.…”