Organoamido- and aryloxo-lanthanoids. xi. Syntheses and crystal structures of nd(odpp)3, nd(odpp)3(thf) and [nd(odpp)3(thf)2].2(thf) (odpp=2, 6-diphenylphenolate): Variations in intramolecular π-ph-nd interactions

Glen B. Deacon, Tiecheng Feng, Brian W Skelton, Allan H White

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The X-ray crystal structure of Nd (Odpp)3 (Odpp = 2, 6-diphenylphenolate), obtained by sublimation of Nd (Odpp)3(thf)2 (thf = tetrahydrofuran) [triclinic, Pī, a 15.835(5), b 13.499(10), c 10.955(11) Å, α 116.25(7), β 92.87(7), γ 101.66(6)°, V 2031 Å3, Z2, No 5726 ‘observed’ data (I > 3σ(I)) refined to conventional R 0.047 shows a near triangular array of oxygens surrounding neodymium ( Nd -O) 2.169 Å, ∑ O- Nd -O 353.2° with additional, intramolecular Nd-η6-Ph chelate interactions ( Nd -C) 3.046 Å and Nd-η1-Ph (Nd -C 2.964(7)Å). There is a pseudotrigonal bipyramidal arrangement of the oxygens, the centroid of the η6-Ph, and the η1-carbon. The complex Nd (Odpp)3(thf), obtained by crystallization of Nd (Odpp)3(thf)2 from toluene (monoclinic, P21/c, a 12.213(4), b 21.447(4), c 17.744Å, β 104.25(2)°, V 4505 Å3, Z 4, R 0.042 for No 8014) also has pseudotrigonal bipyramidal stereochemistry, with a triangular equatorial array of aryl oxide oxygens ( Nd -O) 2.193 Å; ∑ O- Nd -O 358.7°, an apical thf oxygen (Nd -O 2.446(3)Å), and an apical intramolecular chelating phenyl group. As the last has three Nd -C contacts (3.094(5), 3.144(5), 3.010(5)Å) significantly shorter than the other three (3.300(5), 3.427(5), 3.377(5)Å), an η3-Ph-Nd interaction seems likely. For [ Nd (Odpp)3(thf)2].2(thf), obtained by crystallization from tetrahydrofuran without drying of the crystals, the X-ray structure (monoclinic, P21, a 10.230(2), b 21.919(5), c 13.411(4) Å, β 101.15(2)°, V 2950 A3, Z2, R 0.058 for No 3237) reveals a distorted trigonal bipyramidal arrangement of three aryl oxide oxygens (two equatorial 2.208(9), 2.16(1) Å; one axial 2.203(9) Å) and two thf oxygens (one equatorial 2.44(1) Å; one axial (significantly distant) 2.62(1) Å). The X-ray structure of [La(Odpp)3(thf)2].2(thf) shows it to be isostructural with the neodymium analogue.

Original languageEnglish
Pages (from-to)741-756
Number of pages16
JournalAustralian Journal of Chemistry
Issue number4
Publication statusPublished - 1995

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