Low coordinate lanthanide(II) complexes supported by bulky guanidinato and amidinato ligands

The preparation of a series of homoleptic, four-coordinate lanthanide(ii) complexes, [Ln(Priso)(2)] (Ln = Sm, Eu or Yb) incorporating the bulky guanidinate ligand Priso(-) ([(ArN)(2)CNPr(i)(2)](-), Ar = 2,6-diisopropylphenyl) is described. X-ray crystallography shows the complexes to be isostructural and to exhibit coordination geometries midway between tetrahedral and planar. Comparisons between the geometries of the complexes and those of the bulkier systems, [Ln(Giso)(2)] (Giso(-) = [(ArN)(2)CNCy(2)](-), Cy = cyclohexyl) are discussed. Attempts to prepare the less hindered amidinate complexes, [Ln(Piso)(2)] (Piso(-) = [(ArN)(2)CBu(t)](-)), were not successful, but did give rise to the heteroleptic complex, [(kappa(1)-N,eta(6)-Piso)Sm(THF)(mu-I)(2)Sm(kappa(1)-N,eta(6)-Piso)]. Whereas the amidinate ligands in this complex chelate the samarium centre in an kappa(1)-N,eta(6)-Ar-fashion, in the closely related complex, [{(kappa(2)-N,N'-Priso)Yb(THF)(mu-I)}(2)], the ytterbium atoms are kappa(2)-N,N'-chelated by the guanidinate ligand. The facility of the planar four-coordinate complex, [Sm(Giso)(2)], to act as a one-electron reducing agent towards a variety of unsaturated substrates has also been explored. The complex has been shown to selectively reductively couple CS(2), via a C-S bond formation, to give the samarium(iii) dimer, [(Giso)(2)Sm(mu-eta(2)-:eta(2)-S(2)CSCS)Sm(Giso)(2)].