Start Over

Molecular Zirconium Nitride Super Base from a Mononuclear Parent Imide.

Authors :: Grant LN
Pinter B
Gu J
Mindiola DJ
Source :: Journal of the American Chemical Society [J Am Chem Soc] 2018 Dec 19; Vol. 140 (50), pp. 17399-17403. Date of Electronic Publication: 2018 Dec 11.
Publication Year :: 2018
Abstract: In this work, we prepared, isolated, and structurally characterized a zirconium complex having a terminally bound imide motif, (PN) <subscript>2</subscript> Zr≡NH (PN <superscript>-</superscript> = (N-(2- <superscript>i</superscript> Pr <subscript>2</subscript> P-4-methylphenyl)-2,4,6-trimethylanilide)), along with the zirconium nitride complex {(PN) <subscript>2</subscript> Zr≡N[μ <subscript>2</subscript> -Li(THF)]} <subscript>2</subscript> . (PN) <subscript>2</subscript> Zr≡NH was prepared by reduction of trans-(PN) <subscript>2</subscript> Zr(N <subscript>3</subscript> ) <subscript>2</subscript> with KC <subscript>8</subscript> . Isotopic labeling and spectroscopic studies were conducted using the respective <superscript>15</superscript> N 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 <superscript>-</superscript> , 1.822(2) Å). It was found that the nitride in {(PN) <subscript>2</subscript> Zr≡N[μ <subscript>2</subscript> -Li(THF)]} <subscript>2</subscript> is super basic and in the range of -36 to -43 p K <subscript>b</subscript> units. Computational studies have been applied to probe the bonding and structure for this new class of zirconium-nitrogen multiple bonds.