Organolanthanide chemistry

Organolanthanide chemistry is the field of chemistry that studies organolanthanides, compounds with a lanthanide-to-carbon bond. Organolanthanide compounds are different from their organotransition metal analogues in the following ways:

They are far more air- and water-sensitive and are often pyrophoric.
Chemistry in the 0 oxidation state is far more limited. In fact, their electropositive nature makes their organometallic compounds more likely to be ionic.
They form no stable carbonyls at room temperature; organolanthanide carbonyl compounds have been observed only in argon matrices, and decompose when heated to 40 K.

σ-Bonded complexes

Metal-carbon σ bonds are found in alkyls of the lanthanide elements such as [LnMe₆]³⁻ and Ln[CH(SiMe₃)₂]₃. Methyllithium dissolved in THF reacts in stoichiometric ratio with LnCl₃ (Ln = Y, La) to yield Ln(CH₃)₃ probably contaminated with LiCl.

If a chelating agent (L-L), such as tetramethylethylenediamine (tmed or tmeda) or 1,2-dimethoxyethane (dme) is mixed with MCl₃ and CH₃Li in THF, this forms [Li(tmed)]₃[M(CH₃)₆] and [Li(dme)]₃[M(CH₃)₆].

Certain powdered lanthanides react with diphenylmercury in THF to yield octahedral complexes:

2 Ln + 3 Ph₂Hg + 6 THF → 2 LnPh₃(THF)₃ + Hg (Ln = Ho, Er, Tm, Lu).

π-Bonded complexes

Cyclopentadienyl complexes, including several lanthanocenes, are known for all lanthanides. All, barring tris(cyclopentadienyl)promethium(III) (Pm(Cp)₃), can be produced by the following reaction scheme:

3 Na[Cp] + MCl₃ → M[Cp]₃ + 3 NaCl

Pm(Cp)₃ can be produced by the following reaction:

2 PmCl₃ + 3 Be[Cp]₂ → 3 BeCl₂ + 2 Pm[Cp]₃

These compounds are of limited use and academic interest.^[1]

References

^ J. J. Zuckerman (17 September 2009). Inorganic Reactions and Methods, The Formation of Bonds to Elements of Group IVB (C, Si, Ge, Sn, Pb). John Wiley & Sons. ISBN 978-0-470-14547-0. Retrieved 28 July 2013.

[Zuckerman2009-1] J. J. Zuckerman (17 September 2009). Inorganic Reactions and Methods, The Formation of Bonds to Elements of Group IVB (C, Si, Ge, Sn, Pb). John Wiley & Sons. ISBN 978-0-470-14547-0. Retrieved 28 July 2013.

[1]

v t e Branches of chemistry
Glossary of chemical formulae List of biomolecules List of inorganic compounds Periodic table
Analytical	Instrumental chemistry Electroanalytical methods Spectroscopy IR Raman UV-Vis NMR Mass spectrometry EI ICP MALDI Separation process Chromatography GC HPLC Crystallography Characterization Titration Wet chemistry Calorimetry Elemental analysis
Theoretical	Quantum chemistry Computational chemistry Mathematical chemistry Molecular modelling Molecular mechanics Molecular dynamics Molecular geometry VSEPR theory
Physical	Electrochemistry Spectroelectrochemistry Photoelectrochemistry Thermochemistry Chemical thermodynamics Surface science Interface and colloid science Micromeritics Cryochemistry Sonochemistry Structural chemistry Chemical physics Molecular physics Femtochemistry Chemical kinetics Spectroscopy Photochemistry Spin chemistry Microwave chemistry Equilibrium chemistry Mechanochemistry
Inorganic	Coordination chemistry Magnetochemistry Organometallic chemistry Organolanthanide chemistry Cluster chemistry Solid-state chemistry Ceramic chemistry
Organic	Stereochemistry Alkane stereochemistry Physical organic chemistry Organic reactions Organic synthesis Retrosynthetic analysis Enantioselective synthesis Total synthesis / Semisynthesis Fullerene chemistry Polymer chemistry Petrochemistry Dynamic covalent chemistry
Biological	Biochemistry Molecular biology Cell biology Chemical biology Bioorthogonal chemistry Medicinal chemistry Pharmacology Clinical chemistry Neurochemistry Bioorganic chemistry Bioorganometallic chemistry Bioinorganic chemistry Biophysical chemistry
Interdisciplinarity	Nuclear chemistry Radiochemistry Radiation chemistry Actinide chemistry Cosmochemistry / Astrochemistry / Stellar chemistry Geochemistry Biogeochemistry Photogeochemistry Environmental chemistry Atmospheric chemistry Ocean chemistry Clay chemistry Carbochemistry Food chemistry Carbohydrate chemistry Food physical chemistry Agricultural chemistry Soil chemistry Chemistry education Amateur chemistry General chemistry Clandestine chemistry Forensic chemistry Forensic toxicology Post-mortem chemistry Nanochemistry Supramolecular chemistry Chemical synthesis Green chemistry Click chemistry Combinatorial chemistry Biosynthesis Chemical engineering Stoichiometry Materials science Metallurgy Ceramic engineering Polymer science
See also	History of chemistry Nobel Prize in Chemistry Timeline of chemistry of element discoveries "The central science" Chemical reaction Catalysis Chemical element Chemical compound Atom Molecule Ion Chemical substance Chemical bond Alchemy Quantum mechanics
Category Commons Portal WikiProject

σ-Bonded complexes

π-Bonded complexes

See also

References

pFad - (p)hone/(F)rame/(a)nonymizer/(d)eclutterfier! Saves Data!