Oxidation of the three-coordinate cerium amide [Ce(N-(SiMe3)2)3] with TeCl4 in toluene solution yields purple, diamagnetic [CeCl(N(SiMe3)2)3], whose structure has been examined by X-ray crystallographic and computational methods.
The reactions of [RuCl 2 (PPh 3 ) 3 ] and ) 2 (η-C 5 H 5 )] with PhCtCSe i Pr provide the selenolatovinylidene complexes [RuCl 2 {dCdC(Se i Pr)Ph}(PPh 3 ) 2 ] and [Ru{dCdC(Se i Pr)Ph}(PPh 3 ) 2 (η-C 5 H 5 )] + . The former, being coordinatively unsaturated, readily reacts with nitrogen and phosphorus donor ligands with retention of the selenolatovinylidene moiety; however, π-acid ligands induce facile elimination of PhCtCSe i Pr.
The synthesis and characterisation of the first neutral cerium dialkyl dithiocarbamate complexes, using a novel oxidative displacement of the amido ligands of [Ce[N(SiMe3)2]3] by tetraalkylthiuram disulfides [R2NC(S)S]2(R = Me, Et) in thf solution, are reported. In the absence of other donors, the complexes [Ce(kappa2-S2CNMe2)3(thf)2] and Ce(kappa2-S2CNEt2)3) 3 were obtained. The addition of a polypyridyl ligand allowed easy access to a range of complexes of general formula [Ce(kappa2-S2CNR2)3(L[intersection]L)][R = Me and L([intersection])L = 2,2'-bipy (4), or 4,7-diphenyl-1,10-phenanthroline (6); or R = Et and L[intersection]L = 2,2'-bipy (5)]. Brief exposure of the Ce(III) dithiocarbamate to oxygen gas afforded in high yield the diamagnetic, crystalline Ce(IV) dithiocarbamate [Ce(kappa2-S2CNEt2)4)] 7. The neodymium (8) and terbium (10) complexes, isoleptic with 2, were prepared from the appropriate 4f metal (Ln) bis(trimethylsilyl)amide [Ln[pN(SiMe3)2]3][Ln = Nd or Tb (9)] and [Me2NC(S)S]2. The structures of the crystalline complexes, 2, 4, 6, 7, 9 and 10 have been determined by X-ray crystallography. Some evidence has been obtained for the formation of the cerium(IV) complex Ce[N(SiMe3)2]2(kappa2-S2CNMe2)2. The cerium(IV) complex 7 has the metal coordinated to eight sulfur atoms of four planar chelating S2CNC2 moities and its geometry is intermediate between dodecahedral and square prismatic; the mean Ce-S bond length of 2.803 A in 7 compares with the 2.950 A in the Ce(III) complex 2.
Octamethyltetrasila[2.2]paracyclophane and [2.2]paracyclophane are prepared in high yield from the Wurtz coupling reaction of [Cr(CO)3{q6-C~fi(SiMe2C1)2'1,4)] and [cr(co),( q6-C6H4(CH2Br)2-1,4)], respectively.
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