Molecular Zirconium Nitride Super Base from a Mononuclear Parent Imide

Grant, Lauren N.; Pinter, Balazs; Gu, Jun; Mindiola, Daniel J.

doi:10.1021/jacs.8b11198

Molecular Zirconium Nitride Super Base from a Mononuclear Parent Imide

Journal Article · Mon Dec 03 04:00:00 EST 2018 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.8b11198· OSTI ID:1843643

^[1]; Pinter, Balazs ^[2]; Gu, Jun ^[3]; ^[3]

Univ. of Pennsylvania, Philadelphia, PA (United States); Program Manager, Catalysis Science Office of Basic Energy Sciences U.S. Department of Energy
Univ. Técnica Federico Santa María, Valparaíso (Chile)
Univ. of Pennsylvania, Philadelphia, PA (United States)

In this work, we prepared, isolated, and structurally characterized a zirconium complex having a terminally bound imide motif, (PN)₂Zr≡NH (PN^– = (N-(2-ⁱPr₂P-4-methylphenyl)-2,4,6-trimethylanilide)), along with the zirconium nitride complex {(PN)₂Zr≡N[μ₂-Li(THF)]}₂. (PN)₂Zr≡NH was prepared by reduction of trans-(PN)₂Zr(N₃)₂ with KC₈. Isotopic labeling and spectroscopic studies were conducted using the respective ¹⁵N enriched isotopologues, whereas solid-state structural studies confirmed some of the shortest Zr≡N distances known to date (Zr≡NH, 1.830(3) Å; Zr≡N^–, 1.822(2) Å). It was found that the nitride in {(PN)₂Zr≡N[μ₂-Li(THF)]}₂ is super basic and in the range of –36 to –43 pK_b units. Furthermore, computational studies have been applied to probe the bonding and structure for this new class of zirconium–nitrogen multiple bonds.

Research Organization:: Univ. of Pennsylvania, Philadelphia, PA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

DOE Contract Number:: SC0012486

OSTI ID:: 1843643

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 50 Vol. 140; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

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