Organolanthanoids XXIII complexes of tris(cyclopentadienyl)lanthanoids with tertiary phosphine oxides and the X-ray crystal structures of [YbCp 3(OPPh 3)] and [NdCp 3(OPBu n3)]

• Published in: Journal of organometallic chemistry Vol. 565; no. 1; pp. 201 - 210
• Main Authors: Deacon, Glen B, Fallon, Gary D, Forsyth, Craig M, Gatehouse, Bryan M, Junk, Peter C, Philosof, Anna, White, Paul A
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 28-08-1998
• Subjects: Cyclopentadienyl; Neodymium; Organolanthanoids; Phosphine oxides; X-ray structure; Ytterbium; Organolanthanoids; Cyclopentadienyl; Neodymium; Phosphine oxides; X-ray structure; Ytterbium
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/S0022-328X(98)00456-2

Treatment of [LnCp
3(THF)] (Ln=La, Nd, Sm, or Yb) (Cp, cyclopentadienyl and THF, tetrahydrofuran) and [Nd(MeCp)
3(THF)] (MeCp, methylcyclopentadienyl) with OPR
3 (R=Ph,
o-tolyl, Bu
n) in either THF or DME (DME, 1,2-dimethoxyethane) gave the complexes [LnCp
3(OPPh
3)] (Ln=La, Nd, Sm and Yb), [Nd(MeCp)
3(OPPh
3)], [SmCp
3(OP(
o-tolyl)
3)], [Nd(MeCp)
3(OP(
o-tolyl)
3)], and [LnCp
3(OPBu
n
3)] (Ln=La, Nd). An attempt to react [GdCp
3(THF)] with OPPh
3 in either THF or DME crystallised unsolvated GdCp
3, whilst a mixture of [GdCp
3(OPPh
3)] and OPPh
3 was recovered from the filtrate. Attempted synthesis of [YbCp
3(OPBu
n
3)] yielded [{YbCp
2(OPBu
n
3)}
2O], the connectivity established by X-ray crystallography, and impure [YbCp
3(OPBu
n
3)]. Single crystal X-ray structure determination of [YbCp
3(OPPh
3)] (monoclinic, space group
P2
1,
a=8.4187(7),
b=17.019(11),
c=9.450(7) Å,
β=97.97(6)°,
Z=2,
R=0.043 for 1576 observed data) showed the complex to contain formal ten coordinate ytterbium with distorted pseudo tetrahedral stereochemistry whilst the structure of [NdCp
3(OPBu
n
3)] (trigonal, space group
P31/
c,
a=
b=12.973(4),
c=9.657(6) Å,
Z=2,
R=0.052 for 602 observed data) showed ten coordinate neodymium with a distinctly trigonal pyramidal arrangement of oxygen and the centroids (Ct) of the Cp rings (Ct–Nd–Ct 119.8°).