Synthesis and Crystal Structure of Ph3Ln(THF)3 (Ln = Er, Tm)

Bochkarev, L. N.; Stepantseva, Tatyana A.; Zakharov, L. N.; Fukin, Georgy K.; Yanovsky, A.I.; Struchkov, Yuri T.

doi:10.1021/om00005a001

Cited by 47 publications

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“…The Tm-C distance of 2.502(5) Å is only the second Tm(III)-C(sp 3 ) distance to be measured crystallographically; the Tm-C distances in (g 2 -C 10 H 14 )TmI(DME) 2 , prepared from the reaction between TmI 2 and anthracene and the only other reported complex containing a Tm(III)-C(sp 3 ) bond, are 2.479(5) and 2.471(6) Å [DME = 1,2-dimethoxyethane] [6]. The Tm-C distance in 6 compares with Tm-C(sp 2 ) distances of 2.421 (6) 2.416(7) Å in Ph 3 Tm(THF) 3 [7] and 2.413(3) Å in (2,6-Ar 2 C 6 H 3 )TmCl 2 (THF) 2 [Ar = 1-naphthyl] [8]. Surprisingly, the difference in the Y-C and Tm-C distances in 5 and 6 (0.045 Å ) is somewhat larger than the difference in ionic radii of Y(III) and Tm(III) [ionic radii for six-coordinate Y(III) 0.900, Tm(III) 0.880 Å [3]].…”

Section: Resultsmentioning

confidence: 88%

σ-Bonded organometallic derivatives of yttrium(III) and thulium(III): An unusual ligand coupling reaction mediated by thulium(III)

Bowman¹,

Izod²,

Clegg³

et al. 2007

Journal of Organometallic Chemistry

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Section: Resultsmentioning

confidence: 88%

σ-Bonded organometallic derivatives of yttrium(III) and thulium(III): An unusual ligand coupling reaction mediated by thulium(III)

Bowman¹,

Izod²,

Clegg³

et al. 2007

Journal of Organometallic Chemistry

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“…Solutions of Eu(C 6 F 5 ) 2 were prepared via a well-established metal-exchange route as outlined in eq 1. 25 After Bochkarev et al already reported in 1995 on the structural characterization of the first phenyl lanthanides with Er and Tm, 26 a third representative of this class of compounds, ScPh 3 (THF) 2 , followed in 1999. 27 Its synthesis involves salt metathesis of ScCl 3 -(THF) 3 with 3 equiv of PhLi.…”

Section: Homoleptic σ-Aryl Complexesmentioning

confidence: 99%

“…δ 214 for the free carbene ligand) and shows a 13 C-89 Y coupling of 33 Hz which indicates that the Y-C bond does not dissociate rapidly on the NMR time scale. 101 The bulkier 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene ( i Pr-Carb) has been used to synthesize a mixed carbene-THF alkyl Lu(CH 2 -SiMe 3 ) 3 (THF)( i Pr-Carb) (26). 22d Due to its higher steric demand, the carbene ligand occupies an equatorial position (Lu-C(Carb) ) 249 pm).…”

Section: Scheme 11 Preparation Of [Arnc(me)chc(me)nar]scme 2 (Thf) Amentioning

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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“…(Ln ϭ Er, Tm)[21] (Figure 1). Likewise, the angles at the samarium atom are considerably bigger for CSm-C (101.1(2)Ϫ107.7(2)°), compared to the angles O-Sm-O (73.84(15)Ϫ80.55(14)°) but the differences in 1 are greater than in the trisaryl compounds (Er: 99.2Ϫ103.5°and 77.7Ϫ80.6°, Tm: 99.8Ϫ102.9°and 79.0Ϫ81.0°) or in hexaoxo-coordinated Ln(OSiPh 3 ) 3 (THF) 3 (Ln ϭ Y: 100.8Ϫ102.3°and 79.6Ϫ82.2°[22]; Ce: 100.4Ϫ103.3°and 76.5Ϫ83.1°[23]).…”

mentioning

confidence: 99%

Organometallic Compounds of the Lanthanides. 157 [1] The Molecular Structure of Tris(trimethylsilylmethyl)samarium, -erbium, -ytterbium, and -lutetium

Schumann

Freckmann

Dechert

2002

Z. anorg. allg. Chem.

114

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SmCl 3 reacts with Me 3 SiCH 2 Li in THF yielding Sm(CH 2 SiMe 3 ) 3 (THF) 3 (1). The single crystal X-ray structural analyses of 1, Er(CH 2 SiMe 3 ) 3 (THF) 2 (2), Yb(CH 2 SiMe 3 ) 3 (THF) 2 (3), and Lu(CH 2 SiMe 3 ) 3 (THF) 2 (4) show the Sm atom in a facoctahedral coordination and the heavier lanthanides Er, Yb, and Metallorganische Verbindungen der Lanthanoide. 157 [1] Die Molekülstruktur von Tris(trimethylsilylmethyl)samarium, -erbium, -ytterbium und -lutetium

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Synthesis and Crystal Structure of Ph3Ln(THF)3 (Ln = Er, Tm)

Cited by 47 publications

References 0 publications

σ-Bonded organometallic derivatives of yttrium(III) and thulium(III): An unusual ligand coupling reaction mediated by thulium(III)

σ-Bonded organometallic derivatives of yttrium(III) and thulium(III): An unusual ligand coupling reaction mediated by thulium(III)

Synthesis and Structural Chemistry of Non-Cyclopentadienyl Organolanthanide Complexes

Organometallic Compounds of the Lanthanides. 157 [1] The Molecular Structure of Tris(trimethylsilylmethyl)samarium, -erbium, -ytterbium, and -lutetium

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