DOI: 10.1002/chem.201002670. Syntheses, Structures, and Reactivities of Homometallic Rare‐Earth‐Metal Multimethyl Methylidene and Oxo Complexes

Syntheses, Structures, and Reactivities of Homometallic Rare‐Earth‐Metal Multimethyl Methylidene and Oxo Complexes

10.1002/chem.201002670

Crossref journal-article

Wiley

Chemistry – A European Journal (311)

Abstract

AbstractUnsolvated, trinuclear, homometallic, rare‐earth‐metal multimethyl methylidene complexes [{(NCN)Ln(μ2‐CH3)}3(μ3‐CH3)(μ3‐CH2)] (NCN=L=[PhC{NC6H4(iPr‐2,6)2}2]−; Ln=Sc (2 a), Lu (2 b)) have been synthesized by treatment of [(L)Ln{CH2C6H4N(CH3)2‐o}2] (Ln=Sc (1 a), Lu (1 b)) with two equivalents of AlMe3 in toluene at ambient temperature in good yields. Treatment of 1 with three equivalents of AlMe3 gives the heterometallic trinuclear complexes [(L)Ln(AlMe4)2] (Ln=Sc (3 a), Lu (3 b)) in good yields. Interestingly, 2 can also be generated by recrystallization of 3 in THF/toluene, thereby indicating that the THF molecule can also induce CH bond activation of 2. Reaction of 2 with one equivalent of ketones affords the trinuclear homometallic oxo–trimethyl complexes [{(L)Ln(μ2‐CH3)}3(μ3‐CH3)(μ3‐O)] (Ln=Sc(4 a), Lu(4 b)) in high yields. Complex 4 b reacts with one equivalent of cyclohexanone to give the methyl abstraction product [{(L)Lu(μ2‐CH3)}3(μ3‐OC6H9)(μ3‐O)] (5 b), whereas reaction of 4 b with acetophenone forms the insertion product [{(L)Lu(μ2‐CH3)}3{μ3‐OCPh(CH3)2}(μ3‐O)] (6 b). Complex 4 a is inert to ketone under the same conditions. All these new complexes have been characterized by elemental analysis, NMR spectroscopy, and confirmed by X‐ray diffraction determination.

Bibliography

Hong, J., Zhang, L., Yu, X., Li, M., Zhang, Z., Zheng, P., Nishiura, M., Hou, Z., & Zhou, X. (2011). Syntheses, Structures, and Reactivities of Homometallic RareâEarthâMetal Multimethyl Methylidene and Oxo Complexes. Chemistry â A European Journal, 17(7), 2130â2137. Portico.

Authors 9

Jianquan Hong (first)
Lixin Zhang (additional)
Xiaying Yu (additional)
Meng Li (additional)
Zhengxing Zhang (additional)
Pengzhi Zheng (additional)
Masayoshi Nishiura (additional)
Zhaomin Hou (additional)
Xigeng Zhou (additional)

References 65 Referenced 75

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The μ3‐CH2and μ3‐CH3groups could not be distinguished in the solid‐state structure of complex2 adue to the crystallographic disorder for bridged carbon atoms. The hydrogen atoms on bridged alkyl groups could not be found in the difference Fourier map but we have identified them through chemical measurement.
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Dates

Type	When
Created	14 years, 8 months ago (Jan. 5, 2011, 9:45 a.m.)
Deposited	1 year, 10 months ago (Oct. 16, 2023, 6:05 a.m.)
Indexed	1 month, 2 weeks ago (July 22, 2025, 6:38 a.m.)
Issued	14 years, 8 months ago (Jan. 5, 2011)
Published	14 years, 8 months ago (Jan. 5, 2011)
Published Online	14 years, 8 months ago (Jan. 5, 2011)
Published Print	14 years, 6 months ago (Feb. 11, 2011)

Funders 0

None

BibTeX

@article{Hong_2011, title={Syntheses, Structures, and Reactivities of Homometallic Rare‐Earth‐Metal Multimethyl Methylidene and Oxo Complexes}, volume={17}, ISSN={1521-3765}, url={http://dx.doi.org/10.1002/chem.201002670}, DOI={10.1002/chem.201002670}, number={7}, journal={Chemistry – A European Journal}, publisher={Wiley}, author={Hong, Jianquan and Zhang, Lixin and Yu, Xiaying and Li, Meng and Zhang, Zhengxing and Zheng, Pengzhi and Nishiura, Masayoshi and Hou, Zhaomin and Zhou, Xigeng}, year={2011}, month=jan, pages={2130–2137} }

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