Two lanthanum(III) complexes containing η²-pyrazolate and η²-1,2,4-triazolate ligands: intramolecular C—H...N/O interactions and coordination geometries

Abstract

The lanthanum(III) complexes tris(3,5-diphenylpyrazolato-κ(2)N,N')tris(tetrahydrofuran-κO)lanthanum(III) tetrahydrofuran monosolvate, [La(C(15)H(11)N(2))(3)(C(4)H(8)O)(3)]·C(4)H(8)O, (I), and tris(3,5-diphenyl-1,2,4-triazolato-κ(2)N(1),N(2))tris(tetrahydrofuran-κO)lanthanum(III), [La(C(14)H(10)N(3))(3)(C(4)H(8)O)(3)], (II), both contain La(III) atoms coordinated by three heterocyclic ligands and three tetrahydrofuran ligands, but their coordination geometries differ. Complex (I) has a mer-distorted octahedral geometry, while complex (II) has a fac-distorted configuration. The difference in the coordination geometries and the existence of asymmetric La-N bonding in the two complexes is associated with intramolecular C-H...N/O interactions between the ligands.

Can Bismuth Replace Mercury in Redox Transmetallation/Protolysis Syntheses from Free Lanthanoid Metals?

“…M.p.128–130 °C; elemental analysis calcd (%) for C 61 H 65 LaN 6 O 4 (1085.11 g mol −1 ): C 67.52, H 6.04, N 7.74; found: C 67.38, H 6.13, N 7.55. 1 crystallized in the orthorhombic space group P 2 1 2 1 2 1 , a =14.108 (3) Å, b =16.241(3) Å, c =22.816 (5) Å, V =5227.8 (19) Å 3 , which is similar to that reported, orthorhombic space group, a =14.146 (3) Å, b =16.358 (3) Å, c =22.856 (5) Å, V =5288.8(18) Å 3 . IR (Nujol): =1604 (m), 1495 (w), 1320 (w), 1295 (m), 1261 (m), 1225 (w), 1180 (m), 1155 (m), 1074 (m), 1027 (s), 971 (s), 916 (m), 868 (m), 800 (m), 762 (s), 722 (m), 696 (m), 685 cm −1 (m).…”

“…IR (Nujol): =1604 (m), 1495 (w), 1320 (w), 1295 (m), 1261 (m), 1225 (w), 1180 (m), 1155 (m), 1074 (m), 1027 (s), 971 (s), 916 (m), 868 (m), 800 (m), 762 (s), 722 (m), 696 (m), 685 cm −1 (m). The 1 H NMR spectrum agreed with that reported …”

“…[La(Ph 2 pz) 3 (thf) 3 ]·thf (1) Colourless crystals (0.234 g, 86 %) were obtained at À20 8Ca fter one week. (3) , c = 22.816 (5) , V = 5227.8 (19) 3 ,w hich is similar to that reported, [41] orthorhombic space group, a = 14.146 ( The 1 HNMR spectrum agreed with that reported. [41] [Ce(Ph 2 pz) 3 (thf) 3 ]·thf (2) Yellow crystals (0.225 g, 83 %) were obtained at À20 8Ca fter two weeks.…”

“…Single crystals of [Ln(Ph 2 pz) 3 (thf) 3 ] ⋅ thf (Ln=La, 1 , Nd, 3 ) were isomorphous and had unit cell parameters in agreement with the respective reported X‐ray data and the cerium complex ( 2 ) was isomorphous with both (see Experimental). Although [Tb(Ph 2 pz) 3 (thf) 3 ] ⋅ thf ( 4 ) is not isomorphous with 1 – 3 , all four complexes have nine coordinate lanthanoid atoms with chelating Ph 2 pz ligands.…”

“…In a further examination of the prospects of utilizing the commercially available BiPh 3 in RTP reactions, Ce and Ho metals were treated with BiPh 3 and t Bu 2 pzH under ultrasonication, but no reaction was achieved. Besides thf coligands,, Ln/Ph 2 pz complexes have been isolated with dme, [22b, 23] 3,5‐diphenylpyrazole, Ph 3 PO or no coligands, and Ln/ t Bu 2 pz complexes have been isolated with py, Ph 3 PO and no coligands . [La(ttfpz) 3 (thf) 3 ] previously been isolated as a hemitoluene solvate and 21 is known, whilst no trivalent lanthanoid complexes of PhMepz have been reported, though divalent [Yb(PhMepz) 2 (dme) 2 ] is known …”