Dalton Transactions

doi: 10.1039/c005456apmid: N/A

doi: 10.1039/c005457gpmid: N/A

doi: 10.1039/c005458ppmid: N/A

doi: 10.1039/c0dt90021dpmid: 20585678

Weiss, Charles J.; Marks, Tobin J.

doi: 10.1039/c003089apmid: 20490409

Lanthanide and actinide catalysts have made significant contributions to many areas of homogeneous catalysis with hydroelementation of C–C unsaturation being a notable area of success. In this Perspective, we review recent advances in f-element hydroelementation for highly selective hydroalkoxylation and hydrothiolation processes. As will be discussed, f-element hydroalkoxylation and hydrothiolation catalysts exhibit selectivities unobtainable by many late transition metal complexes. First, we review lanthanide-mediated hydroalkoxylation processes with mechanistic, thermodynamic, and kinetic considerations discussed, and then compare/contrast them with analogous C–N and C–P bond-forming transformations. In addition, computational studies are discussed which provide further insight into this transformation and the observed selectivities. Next, actinide-mediated alkyne hydrothiolation is reviewed with a similar discussion of reactivity, mechanism, and thermodynamics.

Nief, François

doi: 10.1039/c001280gpmid: 20631944

The synthesis of non-classical divalent lanthanide complexes, i.e. those not containing the classical samarium(ii), europium(ii) or ytterbium(ii), was once thought impossible. Since 1997, when the first stable complex of thulium(ii) was discovered, there has been many more examples of stable coordination and organometallic complexes of lanthanum(ii), neodymium(ii) and dysprosium(ii) in addition to thulium(ii), and the influence of the ligand system on the stability of the complexes is beginning to be understood. These non-classical divalent compounds show exceptional reactivity as some of them have been shown to activate dinitrogen at room temperature, together with related reduced divalent-like systems, and to undergo spontaneous intramolecular carbon–hydrogen bond activation. Many more examples of non-classical divalent compounds together with new aspects of their exciting reactivity should be discovered in the near future.

Katkova, Marina A.; Bochkarev, Mikhail N.

doi: 10.1039/c001152epmid: 20390195

The metal–organic complexes of Sc, Y, La and lanthanides, which were tested as luminescent materials in organic light emitting diodes (OLEDs), are collected. The performances of the devices are given. Advantages and drawbacks of organic derivatives of rare earth metals as emissive materials are considered.

Satapathy, Rashmirekha; Dash, Barada Prasanna; Maguire, John A.; Hosmane, Narayan S.

doi: 10.1039/c001994apmid: 20383406

The role of carborane clusters in organometallic chemistry is diverse. A number of carborane cage systems such as C2B4, C2B9 and C2B10 clusters have been extensively used for the synthesis of numerous metallacarboranes of s, p, d and f-block elements. An introduction to the chemistry of metallacarboranes is provided with an emphasis on the recent advances on the metallacarboranes of f-block elements.

Cruz, Carlos A.; Emslie, David J. H.; Jenkins, Hilary A.; Britten, James F.

doi: 10.1039/c002122apmid: 20631945

Methyl and n-butyl thorium complexes of a rigid 2,6-bis(anilidomethyl)pyridine ligand have been prepared; the n-butyl complex is thermally stable, even at 60 °C, while the methyl complexes exhibit a high tendency to eliminate methane viaσ-bond metathesis.

Lorenz, Volker; Blaurock, Steffen; Hrib, Cristian G.; Edelmann, Frank T.

doi: 10.1039/c0dt00094apmid: 20548992

Treatment of [(COT)Nd(THF)2(μ-Cl)]2 with dilithium tetraphenyldisiloxanediolate, (LiOSiPh2)2O, in a molar ratio of 1 : 4 afforded the novel organic/inorganic triple-decker complex (μ-η8:η8-COT)[Nd{(Ph2SiO)2O}2{Li(THF)2}{Li(THF)}]2 (1) which was structurally characterized by X-ray diffraction.