Source:http://linkedlifedata.com/resource/pubmed/id/18816050
| Subject | Predicate | Object | Context |
|---|---|---|---|
| pubmed-article:18816050 | rdf:type | pubmed:Citation | lld:pubmed |
| pubmed-article:18816050 | lifeskim:mentions | umls-concept:C0025552 | lld:lifeskim |
| pubmed-article:18816050 | lifeskim:mentions | umls-concept:C0220781 | lld:lifeskim |
| pubmed-article:18816050 | lifeskim:mentions | umls-concept:C1516769 | lld:lifeskim |
| pubmed-article:18816050 | lifeskim:mentions | umls-concept:C1704241 | lld:lifeskim |
| pubmed-article:18816050 | lifeskim:mentions | umls-concept:C1883254 | lld:lifeskim |
| pubmed-article:18816050 | lifeskim:mentions | umls-concept:C0678594 | lld:lifeskim |
| pubmed-article:18816050 | lifeskim:mentions | umls-concept:C2603343 | lld:lifeskim |
| pubmed-article:18816050 | lifeskim:mentions | umls-concept:C1880157 | lld:lifeskim |
| pubmed-article:18816050 | lifeskim:mentions | umls-concept:C1517004 | lld:lifeskim |
| pubmed-article:18816050 | lifeskim:mentions | umls-concept:C1611588 | lld:lifeskim |
| pubmed-article:18816050 | pubmed:issue | 20 | lld:pubmed |
| pubmed-article:18816050 | pubmed:dateCreated | 2008-10-14 | lld:pubmed |
| pubmed-article:18816050 | pubmed:abstractText | Synthesis, structure, and reactivity of two families of rare-earth metal complexes containing discrete methyl cations [LnMe(2-x)(thf)n]((1+x)+) (x = 0, 1; thf = tetrahydrofuran) have been studied. As a synthetic equivalent for the elusive trimethyl complex [LnMe3], lithium methylates of the approximate composition [Li3LnMe6(thf)n] were prepared by treating rare-earth metal trichlorides [LnCl3(thf)n] with 6 equiv of methyllithium in diethyl ether. Heteronuclear complexes of the formula [Li3Ln2Me9L(n)] (Ln = Sc, Y, Tb; L = Et2O, thf) were isolated by crystallization from diethyl ether. Single crystal X-ray diffraction studies revealed a heterometallic aggregate of composition [Li3Ln2Me9(thf)n(Et2O)m] with a [LiLn2Me9](2-) core (Ln = Sc, Y, Tb). When tris(tetramethylaluminate) [Ln(AlMe4)3] (Ln = Y, Lu) was reacted with less than 1 equiv of [NR3H][BPh4], the dimethyl cations [LnMe2(thf)n][BPh4] were obtained. The coordination number as well as cis/trans isomer preference was studied by crystallographic and computational methods. Dicationic methyl complexes of the rare-earth metals of the formula [LnMe(thf)n][BAr4]2 (Ln = Sc, Y, La-Nd, Sm, Gd-Lu; Ar = Ph, C6H4F-4) were synthesized, by protonolysis of either the ate complex [Li3LnMe6(thf)n] (Ln = Sc, Y, Gd-Lu) or the tris(tetramethylaluminate) [Ln(AlMe4)3] (Ln = La-Nd, Sm, Dy, Gd) with ammonium borates [NR3H][BAr4] in thf. The number of coordinated thf ligands varied from n = 5 (Ln = Sc, Tm) to n = 6 (Ln = La, Y, Sm, Dy, Ho). The configuration of representative examples was determined by X-ray diffraction studies and confirmed by density-functional theory calculations. The highly polarized bonding between the methyl group and the rare-earth metal center results in the reactivity pattern dominated by the carbanionic character and the pronounced Lewis acidity: The dicationic methyl complex [YMe(thf)6](2+) inserted benzophenone as an electrophile to give the alkoxy complex [Y(OCMePh2)(thf)5](2+). Nucleophilic addition of the soft anion X(-) (X(-) = I(-), BH4(-)) led to the monocationic methyl complexes [YMe(X)(thf)5](+). | lld:pubmed |
| pubmed-article:18816050 | pubmed:language | eng | lld:pubmed |
| pubmed-article:18816050 | pubmed:journal | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:18816050 | pubmed:status | PubMed-not-MEDLINE | lld:pubmed |
| pubmed-article:18816050 | pubmed:month | Oct | lld:pubmed |
| pubmed-article:18816050 | pubmed:issn | 1520-510X | lld:pubmed |
| pubmed-article:18816050 | pubmed:author | pubmed-author:EisensteinOdi... | lld:pubmed |
| pubmed-article:18816050 | pubmed:author | pubmed-author:OkudaJunJ | lld:pubmed |
| pubmed-article:18816050 | pubmed:author | pubmed-author:ArndtStefanS | lld:pubmed |
| pubmed-article:18816050 | pubmed:author | pubmed-author:RobertDominiq... | lld:pubmed |
| pubmed-article:18816050 | pubmed:author | pubmed-author:SpaniolThomas... | lld:pubmed |
| pubmed-article:18816050 | pubmed:author | pubmed-author:MaronLaurentL | lld:pubmed |
| pubmed-article:18816050 | pubmed:author | pubmed-author:ZeimentzPeter... | lld:pubmed |
| pubmed-article:18816050 | pubmed:author | pubmed-author:KramerMathias... | lld:pubmed |
| pubmed-article:18816050 | pubmed:author | pubmed-author:YahiaAhmedA | lld:pubmed |
| pubmed-article:18816050 | pubmed:issnType | Electronic | lld:pubmed |
| pubmed-article:18816050 | pubmed:day | 20 | lld:pubmed |
| pubmed-article:18816050 | pubmed:volume | 47 | lld:pubmed |
| pubmed-article:18816050 | pubmed:owner | NLM | lld:pubmed |
| pubmed-article:18816050 | pubmed:authorsComplete | Y | lld:pubmed |
| pubmed-article:18816050 | pubmed:pagination | 9265-78 | lld:pubmed |
| pubmed-article:18816050 | pubmed:year | 2008 | lld:pubmed |
| pubmed-article:18816050 | pubmed:articleTitle | Cationic methyl complexes of the rare-earth metals: an experimental and computational study on synthesis, structure, and reactivity. | lld:pubmed |
| pubmed-article:18816050 | pubmed:affiliation | Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, D-52074 Aachen, Germany. | lld:pubmed |
| pubmed-article:18816050 | pubmed:publicationType | Journal Article | lld:pubmed |