Organolanthanoids. III. Preparations and properties of some Di(alkynyl)lanthanoids

Deacon, Glen B.; Koplick, Andrew J.; Tuong, Tran Dinh

doi:10.1071/ch9820941

Cited by 33 publications

(29 citation statements)

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“…Alkynyl derivatives of divalent europium and ytterbium are also available via transmetalation reactions in which Hg(CtCR) 2 is reacted with the corresponding metals according to eq 33. 108,109 In the case of trivalent lanthanides the tris-(alkynyl) complexes Lu(CtCtBu) 3 110 and Ln(Ct CPh) 3 (Ln ) Pr, Sm, Eu, Gd, Tb, Er, Yb) 111,112 have been described. Although virtually nothing is known about the molecular structures of all these compounds, it is very likely, however, that the unsolvated species Ln(CtCR) 2 and Ln(CtCR) 3 are polymeric materials with bridging alkynyl ligands.…”

Section: Alkenyl and Alkynyl Complexesmentioning

confidence: 99%

Synthesis and Structural Chemistry of Non-Cyclopentadienyl Organolanthanide Complexes

2002

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Over the years one major challenge has remained in organolanthanide chemistry: the synthesis of homoleptic alkyl and aryl complexes. The simplest organometallic compounds of the rare earths are the species LnR 2 or LnR 3 with the rare earth metals in their common oxidation states Ln 2+ and Ln 3+ which imply the coordination of only two or three ligands to the metal center. This is usually insufficient to meet the lanthanides' demands of steric saturation through high coordination numbers.Hence for a long time, only indirect evidence could be found for the existence of simple homoleptic organolanthanide compounds; the isolation and characterization of compounds belonging to this class were first achieved recently using pentafluorophenyl for Ln 2+ derivatives 12 and very bulky alkyl ligands for Ln 3+ species. [13][14][15] Especially for alkyls, very little structural data are available for compounds without any trimethylsilyl-substituted ligands which generally ensure higher stability. But nevertheless, due to the difficulties of their synthesis and their high reactivity alkyls and aryls still represent an interesting class of compounds. 16 Homoleptic σ-Alkyl ComplexesShortly after the synthesis of the first divalent solvent-free Ln alkyl, [(Me 3 Si) 3 C] 2 Yb, 17 the Eu analogue was prepared similarly by the reaction of EuI 2 and KC(SiMe 3 ) 3 in benzene. 18 It also features the bent structure displayed by the Yb complex but with a slightly smaller C-Eu-C angle (C-Eu-C ) 136°, C-Yb-C ) 137°) and longer Eu-C bonds (Eu-C ) 261 pm, Yb-C ) 249/250 pm). Salt metathesis was then again applied successfully to synthesize the first divalent Sm alkyl, Sm[C(SiMe 3 ) 2 (SiMe 2 OMe)] 2 (THF) Frank T. Edelmann was born in Hamburg, Germany, in 1954. He studied chemistry from 1974 to 1979 at the University of Hamburg, where he obtained his Diplom in 1979 and doctoral degree in 1983. His Ph.D. thesis entitled "The chemistry of the tricarbonyl(fulvene) chromium complexes" was carried out under the supervision of Prof. Ulrich Behrens. This was followed by two years (1983−1985) of postdoctoral research as a Feodor Lynen Fellow of the Alexander-von-Humboldt Foundation in the groups of Professors Josef Takats (

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Section: Alkenyl and Alkynyl Complexesmentioning

confidence: 99%

Synthesis and Structural Chemistry of Non-Cyclopentadienyl Organolanthanide Complexes

2002

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“…Homoleptic phenylethynyl compounds of lanthanides (PhC≡C) 2 Ln and (PhC≡C) 3 Ln (Ln standing for a lanthanide) are notable for the presence of the reactive metal-carbon bond and the unsaturated ligand, the latter acting as the second active center of the molecule; hence, such compounds are bifunctional reagents suitable for various organoelement syntheses. Even though certain representatives of this class have been known for long [1], their wide application has been limited by the absence of the convenient preparation methods.…”

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“…They have been prepared for the first time via transmetalation of organomercury compounds [Eq. (1)] [2,3] and the acid-base interaction of phenylacetylene with bis(pentafluorophenyl)-or bis(tert-butylethynyl)ytterbium [Eq. (3)] [2].…”

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confidence: 99%

“…The products were dark-colored pyrophoric amorphous compounds decomposing upon heating above 200°С, soluble in 1,2-dimethoxyethane, tetrahydrofuran, and benzene, readily hydrolysable to give phenylacetylene and Ln(OH) 3 . IR spectra of the prepared (PhC≡C) 3 Ln were similar to that of tri(phenylethynyl)scandium [5].…”

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confidence: 99%

“…The hydrolysis was accompanied by oxidation of the lanthanides atoms and formation of the Ln(OH) 3 hydroxide, and the evolving hydrogen favored the ketones transformation into the pinacones.…”

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