Cerium(III) dialkyl dithiocarbamates from [Ce[N(SiMe3)2]3] and tetraalkylthiuram disulfides, and [Ce(kappa2-S2CNEt2)4] from the Ce(III) precursor; Tb(III) and Nd(III) analogues.

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)].

Oxidation in nonclassical organolanthanide chemistry: synthesis, characterization, and X-ray crystal structures of cerium(III) and -(IV) amides.

[Ce(NR(2))(3)] (R = SiMe(3)) with TeCl(4) in tetrahydrofuran solution gave a mixture of two major products in a combined yield of ca. 50% based on available metal: (i) the Ce(IV) amide [CeCl(NR(2))(3)] (1), which was isolated as purple needles and identified on the basis of (1)H NMR and mass spectra, microanalysis, and a single-crystal X-ray analysis [C(18)H(54)CeClN(3)Si(6), rhombohedral, R3c (No. 161), a = b = 18.

Cerium masquerading as a group 4 element: synthesis, structure and computational characterisation of [CeCl(N(SiMe3)2)3].

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.

Tetravalent Tellurium Ligands.

Oxidative addition of TeCl to Vaska's complex gave the trichlorotelluronium complex [IrCl (TeCl )(CO)(PPh ) ] (structure depicted), which contains a rare example of a structurally characterized tetravalent tellurium ligand. The coordination at the Te center is-in full agreement with the VSEPR model-distorted trigonal bipyramidal.

Alkylidyne-Metal Templated Triboronate Condensation.

Under exceptionally mild conditions the alkylidyne metallatetraborane 1 undergoes an intriguing conversion into the dodecaboronate dianion in a rare example of metal-templated boronate condensation.