ORGANOAMIDO-LANTHANOIDS AND ARYLOXO-LANTHANOIDS .11. 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 PI-PH-ND INTERACTIONS

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, P (1) over bar, a 15 . 835(5), b 13 . 499(10), c 10 . 955(11)Angstrom, alpha 116 . 25(7), beta 92 . 87(7), gamma 101 . 66(6)degrees, V 2031 Angstrom(3) Z 2, N-o 5726 'observed' data (I > 3 sigma(I)) refined to conventional R 0 . 047] shows a near triangular array of oxygens surrounding neodymium (Nd-O) 2 . 16(9) Angstrom, Sigma O-Nd-O 353 .(2) degrees with additional, intramolecular Nd-eta(6)-Ph chelate interactions [Nd-C] 3 . 04(6) Angstrom and Nd-eta(1)-Ph (Nd-C 2 . 964(7) Angstrom). There is a pseudotrigonal bipyramidal arrangement of the oxygens, the centroid of the eta(6)-Ph, and the eta(1)-carbon. The complex Nd(Odpp)(3)(thf), obtained by crystallization of Nd(Odpp)(3)(thf)(2) from toluene (monoclinic, P2(1)/c, a 12 . 213(4), b 21 . 447(4), c 17 . 744 Angstrom, beta 104 . 25(2)degrees, V 4505 Angstrom(3), Z 4, R 0 . 042 for N-o 8014) also has pseudotrigonal bipyramidal stereochemistry, with a triangular equatorial array of aryl oxide oxygens [Nd-O] 2 . 19(3) Angstrom; Sigma O-Nd-O 358 .(7) degrees, an apical thf oxygen (Nd-O 2 . 446(3) Angstrom), and an apical intramolecular chelating phenyl group. As the last has three Nd-C contacts (3 . 094(5), 3 . 144(5), 3 . 010(5) Angstrom) significantly shorter than the other three (3 . 300(5), 3 . 427(5), 3 . 377(5) Angstrom), an eta(3)-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, P2(1), a 10 . 230(2), b 21 . 919(5), c 13 . 411(4) Angstrom,beta 101 . 15(2)degrees, V 2950 Angstrom(3), Z 2, R 0 . 058 for N-o 3237) reveals a distorted trigonal bipyramidal arrangement of three aryl oxide oxygens (two equatorial 2 . 208(9), 2 . 16(1) Angstrom; one axial 2 . 203(9) Angstrom) and two thf oxygens (one equatorial 2 . 44(1) Angstrom; one axial (significantly distant) 2 . 62(1)Angstrom). The X-ray structure of [La(Odpp)(3) (thf)(2)].2(thf) shows it to be isostructural with the neodymium analogue.