Divalent -Octaphenyllanthanocenes: Synthesis, Structures, and Eu Luminescence.

Reductive dimerization of fulvenes using low-valent metal precursors is a straightforward one-step approach to access ethylene-bridged metallocenes. This process has so far mainly been employed with fulvenes carrying one or two substituents in the exocyclic position. In this work, a new synthesis of the unsubstituted exocyclic 1,2,3,4-tetraphenylfulvene (), its full structural characterization by NMR spectroscopy and single-crystal X-ray diffraction, as well as some photophysical properties and its first use in reductive dimerization are described.

Selective carbon-phosphorus bond cleavage: expanding the toolbox for accessing bulky divalent lanthanoid sandwich complexes.

The synthesis of two new tetra- and penta-phenycyclopentadienyldiphenylphosphine pro-ligands which readily undergo selective C-P bond cleavage has allowed for the facile synthesis of bulky divalent octa- and deca-phenylmetallocenes of europium, ytterbium and samarium.

Lanthanoid Biphenolates as a Rich Source of Lanthanoid-Main Group Heterobimetallic Complexes.

Several new trivalent dinuclear rare earth 2,2'-methylenebis(6-tert-butyl-4-methylphenolate) (mbmp ) complexes with the general form [Ln (mbmp) (thf) ] (Ln=Sm 1, Tb 2 (n=3), and Ho 3, Yb 4 (n=2), and a tetravalent cerium complex [Ce(mbmp) (thf) ] (5) have been synthesised by RTP (redox transmetallation/protolysis) reactions from lanthanoid metals, Hg(C F ) and the biphenol mbmpH . These new complexes and some previously reported partially protonated rare earth biphenolate complexes [Ln(mbmp)(mbmpH)(thf) ] react with lithium, aluminium, potassium and zinc organometallic reagents to form lanthanoid-main group heterobimetallic species. When reaction mixtures containing the Ln biphenolate complexes were treated with n-butyllithium, both molecular ([Li(thf) Ln(mbmp) (thf) ] (Ln=La 6, Pr 7 (n=2) and Er 8, Yb 9, and Lu 10 (n=1)) and charge separated ([Li(thf) ][Ln(mbmp) (thf) ] (Ln=Y 11, Sm 12, Dy 13, and Ho 14) complexes were isolated.

New lanthanoid biphenolate complexes, their further reactivity with trimethylaluminium and catalytic activity for the polymerisation of -lactide.

A series of rare earth biphenolate complexes of the general form [Ln(mbmp)(mbmpH)(thf)] (Ln = Y (1), Nd (2), Gd (3), Dy (4), Er (5), Tm (6) and Lu (7)) have been synthesised by redox transmetallation/protolysis (RTP) from the free rare earth metal, Hg(CF) and 2,2'-methylenebis(6--butyl-4-methylphenol) (mbmpH). The rare earth metal is six coordinate with one chelating biphenolate mbmp ligand and one unidentate monophenolate mbmpH ligand. The yttrium complex, when crystallised from hot toluene or deuterated benzene, loses a coordinated thf and exhibits coordination through all three phenolate oxygen atoms, as well as the oxygen of the phenol, yielding two solvates [Y(mbmp)(mbmpH)(thf)]·solv (solv = PhMe, = 1 (8a) or CD, = 2 (8b)).