Using Diamagnetic Yttrium and Lanthanum Complexes to Explore Ligand Reduction and C-H Bond Activation in a Tris(aryloxide)mesitylene Ligand System

Palumbo CT, Halter D, Voora VK, Chen GP, Ziller JW, Gembicky M, Rheingold AL, Furche F, Meyer K, Evans WJ (2018)

Publication Type: Journal article

Publication year: 2018

Journal

Inorganic Chemistry American Chemical Society

Book Volume: 57

Pages Range: 12876-12884

Journal Issue: 20

DOI: 10.1021/acs.inorgchem.8b02053

Abstract

[Y(N(SiMe3)2)3] reacts with (Ad,MeArOH)3mes to form the Y3+ complex [((Ad,MeArO)3mes)Y], 1-Y. This complex reacts with potassium metal in the presence of 2.2.2-cryptand to give a cocrystallized mixture of [K(2.2.2-cryptand)][((Ad,MeArO)3mes)Y], 2-Y, and [K(2.2.2-cryptand)][((Ad,MeArO)3mes)YH], 3-Y. The electron paramagnetic resonance spectrum of this crystalline mixture exhibits an isotropic signal at 77 K (giso = 2.000, Wiso = 1.8 mT), suggesting that 2-Y is best described as a Y3+ complex of the tris(aryloxide)mesitylene radical ((Ad,MeArO)3mes)4-. Evidence of the hydride ligand in 3-Y was obtained by 89Y-1H heteronuclear multiple quantum coherence NMR spectroscopy, and a coupling constant of JYH = 93 Hz was observed. A single crystal of 3-Y was also obtained in pure form and structurally characterized for comparison with the crystal data on the mixed component 2-Ln/3-Ln crystals. The origin of the hydride in 3-Ln is unknown, but further studies of the reduction of 1-La, previously found to form 2-La, revealed a possible source. Ligand-based C-H bond activation and loss of hydrogen can occur under reducing conditions to form a tetraanionic ligand derived from ((Ad,MeArO)3mes)3-, as observed in [K(2.2.2-cryptand)][((Ad,MeArO)3(C6Me3(CH2)2CH)La], 4-La.

Authors with CRIS profile

Dominik Halter Lehrstuhl für Anorganische und Allgemeine Chemie Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

University of California Irvine US United States (USA) (US) University of California, San Diego US United States (USA) (US)

How to cite

APA:

Palumbo, C.T., Halter, D., Voora, V.K., Chen, G.P., Ziller, J.W., Gembicky, M.,... Evans, W.J. (2018). Using Diamagnetic Yttrium and Lanthanum Complexes to Explore Ligand Reduction and C-H Bond Activation in a Tris(aryloxide)mesitylene Ligand System. Inorganic Chemistry, 57(20), 12876-12884. https://dx.doi.org/10.1021/acs.inorgchem.8b02053

MLA:

Palumbo, Chad T., et al. "Using Diamagnetic Yttrium and Lanthanum Complexes to Explore Ligand Reduction and C-H Bond Activation in a Tris(aryloxide)mesitylene Ligand System." Inorganic Chemistry 57.20 (2018): 12876-12884.

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