Lutetium gets a crown: Synthesis, structure and reaction chemistry of the separated ion pair complex, [Li(12-crown-4)2][(C5Me5)2LuMe2]

Thomson, Robert K.; Monreal, Marisa J.; Masuda, Jason D.; Scott, Brian L.; Kiplinger, Jaqueline L.

doi:10.1016/j.jorganchem.2011.06.017

Cited by 12 publications

(6 citation statements)

References 55 publications

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“…The occurrence of this structural motif is unexpected as μ-coordinating alkynyl ligands are very well-documented, e.g., for related phosphine Cu I complexes . However, the ions [(PhCC) 2 Cu] − and [(NHC) 2 Cu] + themselves have also been reported independently …”

Section: Resultsmentioning

confidence: 91%

[(NHC)Cu^I–ER₃] Complexes (ER₃ = SiMe₂Ph, SiPh₃, SnMe₃): From Linear, Mononuclear Complexes to Polynuclear Complexes with Ultrashort Cu^I···Cu^I Distances

Plotzitzka

Kleeberg

2016

Inorg. Chem.

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A series of complexes of the type [(NHC)Cu-ER3] (NHC = IDipp, IMes, ItBu, Me2IMe, and ER3 = SiMe2Ph, SiPh3, SnMe3) and [(NHC)Cu-R'] (NHC = IDipp, Me2IMe and R' = Ph, C≡CPh) was synthesized in good yields by the reaction of the corresponding [(NHC)Cu-OtBu] complex with the respective silylborane pinB-ER3 (pin = OCMe2CMe2O; ER3 = SiMe2Ph, SiPh3), the stannylborane ((C2H4)(iPrN)2)B-SnMe3, or a boronic acid ester pinB-R' (R' = Ph, C≡CPh). Solid structures of all complexes were systematically studied by X-ray diffraction analysis. The solid state structures of the complexes [(NHC)Cu-ER3] show a dependence of the structural motif from the steric properties of the NHC ligand. The sterically demanding NHC ligands (IDipp, IMes, ItBu) lead to monomeric, linear complexes [(NHC)Cu-ER3], while with the less demanding Me2IMe ligand, polynuclear, μ-ER3-bridged complexes with ultrashort Cu···Cu distances are observed. For the related complexes [(NHC)Cu-R'] no analogous complexes with bridging anionic ligands are realized. Instead, irrespective of the NHC ligand, linear coordinated copper complexes of different types are formed. (29)Si heteronuclear solution NMR spectroscopic data on [(NHC)Cu(I)-SiR3] exhibit distinctly different chemical shifts for the (in the solid state) monomeric and dimeric complexes suggesting different structure types also in solution. This agrees well with the observation of a trinuclear complex [(Me2IMe)Cu-SnMe3]3 both in the solid state and in solution. Initial catalytic studies suggest that [(NHC)Cu-OtBu] complexes (NHC = ItBu, Me2IMe) are, in addition to the established [(IDipp)Cu-OtBu] complex, efficient precatalysts for the silylation of aldehydes and α,β-unsaturated ketones with pinB-SiMe2Ph.

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Section: Resultsmentioning

confidence: 91%

[(NHC)Cu^I–ER₃] Complexes (ER₃ = SiMe₂Ph, SiPh₃, SnMe₃): From Linear, Mononuclear Complexes to Polynuclear Complexes with Ultrashort Cu^I···Cu^I Distances

Plotzitzka

Kleeberg

2016

Inorg. Chem.

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“…A π‐electron interaction between the triple bond and the atomic orbitals of the rare‐earth‐metal atom should also be observable by a lengthening of the triple bond. In terminally bonded phenylacetylides, the CC bond is about 1.2 Å (e.g., 1.19(1) and 1.21(1) Å in [Cp*Lu(CCPh) 2 (bipy)(py)]8c and 1.204(12) Å for both triple bonds in the ate‐complex of lutetium, [Li(12‐crown‐4) 2 ][(Cp*) 2 Lu(CCPh) 2 ]) 9c. As a non‐coordinated anion, the [AlMe 2 (CCPh) 2 ] − ligand shows CC bond lengths of 1.204(4) and 1.233(5) Å 16…”

Section: Resultsmentioning

confidence: 99%

Rare‐Earth‐Metal Dialkynyl Dimethyl Aluminates

Nieland

Mix

Neumann

et al. 2013

Chemistry A European J

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A new class of rare-earth-metal alkynyl complexes has been prepared. The reactions of the tris(tetramethylaluminate)s of lanthanum, praseodymium, samarium, yttrium, holmium, and thulium, [Ln(AlMe₄)₃], with phenylacetylene afforded compounds [Ln{(μ-C≡CPh)₂AlMe₂}₃] (Ln=La (1), Pr (2), Sm (3), Y (4), Ho (5), Tm (6)). All of these compounds have been characterized by NMR spectroscopy, X-ray crystallography, and by elemental analysis. NMR spectroscopic studies of the series of para- magnetic compounds [Ln(AlMe₄)₃] and [Ln{(μ-C≡CPh)₂AlMe₂}₃] have also been performed.

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“…The title compound was prepared according to a procedure adapted from the literature. 43 1,2,3,4,54.6 mmol,1.0 equiv) was added dropwise to a stirred solution of sodium bis(trimethylsilyl)amide (9.17 g, 50.0 mmol, 0.92 equiv) in Et 2 O (45 mL), and the opaque suspension was allowed to stir for 18 h. After this time, the solid product was collected by vacuum filtration, washed with Et 2 O (2 × 5 mL) and pentane (2 × 10 mL), and dried in vacuo to give a white solid (5.69 g, 40.0 mmol, 72% yield). Spectral data are consistent with those previously reported.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…Spectral data are consistent with those previously reported. 43 Synthesis of (n-Bu) 3 SnCp* (28). The title compound was prepared according to a procedure adapted from the literature.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Experimental and Computational Evaluation of Tantalocene Hydrides for C–H Activation of Arenes

2021

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Half a century ago, tantalocene hydrides (especially Cp2TaH3, where Cp = η5-C5H5) were reported to catalyze H/D exchange with arenes. However, there has been very little follow-up to the seminal reports, and numerous questions about this chemistry remain unanswered. In an effort to better evaluate the potential of tantalocene hydrides for processes involving C–H activation, we have conducted a series of experimental and computational studies on these complexes. Density functional theory (DFT) calculations support a mechanism for arene C–H activation involving oxidative addition at transient TaIII, rather than a σ-bond metathesis mechanism at TaV. Comparisons were made between thermal and photochemical conditions for the reaction of Cp2TaH3 with benzene-d 6, and H/D exchange was found to be moderately faster under thermal conditions. In a reaction with toluene, Cp2TaH3 activates the aromatic C(sp 2 )–H bonds but not the benzylic bonds. DFT calculations suggest that benzylic C–H activation at TaIII has a barrier similar to aromatic C–H activation, but that formation of a π-complex with Cp2TaH directs preferential aromatic C–H activation. Analogous complexes containing the less labile permethylated ligand Cp* (Cp* = η5-C5Me5) were also evaluated for their ability to catalyze H/D exchange with benzene-d 6, but these complexes are less active than Cp2TaH3. DFT calculations indicate that the methyl groups of Cp* disfavor π-coordination of an arene to the TaIII intermediate.

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Lutetium gets a crown: Synthesis, structure and reaction chemistry of the separated ion pair complex, [Li(12-crown-4)2][(C5Me5)2LuMe2]

Cited by 12 publications

References 55 publications

[(NHC)Cu^I–ER₃] Complexes (ER₃ = SiMe₂Ph, SiPh₃, SnMe₃): From Linear, Mononuclear Complexes to Polynuclear Complexes with Ultrashort Cu^I···Cu^I Distances

[(NHC)Cu^I–ER₃] Complexes (ER₃ = SiMe₂Ph, SiPh₃, SnMe₃): From Linear, Mononuclear Complexes to Polynuclear Complexes with Ultrashort Cu^I···Cu^I Distances

Rare‐Earth‐Metal Dialkynyl Dimethyl Aluminates

Experimental and Computational Evaluation of Tantalocene Hydrides for C–H Activation of Arenes

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Lutetium gets a crown: Synthesis, structure and reaction chemistry of the separated ion pair complex, [Li(12-crown-4)2][(C5Me5)2LuMe2]

Cited by 12 publications

References 55 publications

[(NHC)CuI–ER3] Complexes (ER3 = SiMe2Ph, SiPh3, SnMe3): From Linear, Mononuclear Complexes to Polynuclear Complexes with Ultrashort CuI···CuI Distances

[(NHC)CuI–ER3] Complexes (ER3 = SiMe2Ph, SiPh3, SnMe3): From Linear, Mononuclear Complexes to Polynuclear Complexes with Ultrashort CuI···CuI Distances

Rare‐Earth‐Metal Dialkynyl Dimethyl Aluminates

Experimental and Computational Evaluation of Tantalocene Hydrides for C–H Activation of Arenes

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Product

Resources

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[(NHC)Cu^I–ER₃] Complexes (ER₃ = SiMe₂Ph, SiPh₃, SnMe₃): From Linear, Mononuclear Complexes to Polynuclear Complexes with Ultrashort Cu^I···Cu^I Distances

[(NHC)Cu^I–ER₃] Complexes (ER₃ = SiMe₂Ph, SiPh₃, SnMe₃): From Linear, Mononuclear Complexes to Polynuclear Complexes with Ultrashort Cu^I···Cu^I Distances