Phosphoraneiminato complexes of rare-earth elements. Crystal structures of [Yb₂Cp₃(NPPh₃)₃], [YCp(NPPh₃)(µ-OSiMe₂NPPh₃)]₂, and [M(NPPh₃)₂(µ-OSiMe₂NPPh₃)]₂ with M = Y and Sm

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Anfang, S. ; Gröb, Thorsten ; Harms, Klaus ; Seybert, Gert ; Massa, Werner ; Greiner, Andreas ; Dehnicke, Kurt:
Phosphoraneiminato complexes of rare-earth elements. Crystal structures of [Yb₂Cp₃(NPPh₃)₃], [YCp(NPPh₃)(µ-OSiMe₂NPPh₃)]₂, and [M(NPPh₃)₂(µ-OSiMe₂NPPh₃)]₂ with M = Y and Sm.
In: Zeitschrift für anorganische und allgemeine Chemie. Bd. 625 (1999) Heft 11 . - S. 1853-1859.
ISSN 1521-3749
DOI: https://doi.org/10.1002/(SICI)1521-3749(199911)625:11<1853::AID-ZAAC1853>3.0.CO;2-4

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Abstract

The ytterbium complex Yb2Cp3(NPPh3)(3)] with sesqui distribution of cyclopentadienide and phosphoraneiminato ligands is made from YbCp2Cl and LiNPPh3 in boiling toluene and isolated as yellow, moisture sensitive crystals, which enclose three molecules of toluene per unit cell. Yb2Cp3(NPPh3)]. 3C(7)H(8) (1): Space group Pbca, Z = 8, lattice dimensions at -80 degrees C: a = 2727.6(2), b = 1977.5(1), c = 2848.9(2) pm; R = 0.0541. Two of the (NPPh3)(-)-groups link the ytterbium atoms to a nonplanar Yb2N2 four-membered ring with a folding angle of 17.1 degrees along the Yb...Yb connecting line. The third (NPPh3)(-) group is terminally bonded with a short Yb-N distance of 214.2 pm. YCp(NPPh3) (mu-OSiMe2NPPh3)](2). 4C(7)H(8) (2) originates from YCpCl2 and LiNPPh3 in boiling toluene with Baysilon-paste participating forming colourless, moisture sensitive crystals. Space group P2(1)/c, Z = 2, lattice dimensions at -80 degrees C: a = 1469.0(1), b = 1234.1(1), c = 2761.5(2)pm, beta = 93.196(10)degrees; R = 0.0518. In 2 the yttrium atoms are linked via the oxygen atoms of the (OSiMe2NPPh3)(-) groups to form a centrosymmetric Y2O2 four-membered ring with Y-O bonds of different lengths. Together with the terminally bonded (NPPh3)(-)-ligand, the eta(5)-C5H5- group, and the N atom of the siloxyphosphaneimine group, which functions as a donor atom, the Y atoms achieve coordination number five. Y(NPPh3)(2)(mu-OSiMe2NPPh3)](2). 2C(7)H(8) (3) and Sm(NPPh3)(2)(mu-OSiMe2NPPh3)](2) (4) originate from the metal trichlorides with KNPPh3 in THF with Baysilon paste participating and subsequent crystallization from toluene as colourless, moisture sensitive crystal needles. 3: Space group P2(1)/n, Z = 2, lattice dimensions at -80 degrees C: a = 1804.1(2), b = 1401.8(1), c = 2221.6(2) pm, beta = 98.716(9)degrees; R = 0.0537. 4: Space group <P(1)over bar >, Z = 1, lattice dimensions at -80 degrees C: a = 1363.4(1), b = 1364.9(1), c = 1650.6(1) pm; alpha = 112.457(8)degrees beta = 91.948(9)degrees, gamma = 114.974(8)degrees; R = 0.0308. 3 and 4 form centrosymmetric dimeric molecules in which the metal atoms are linked via the oxygen atoms of the (OSiMe2NPPh3)(-) groups to form M2O2 four-membered rings with M-O bonds of varying length. Together with the terminally bonded (NPPh3)(-) ligands and the N atom of the siloxyphosphaneimine ligand, which functions as a donor atom, the metal atoms achieve coordination number five.