Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 140, Issue 50, Pages 17399-17403Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b11198
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Funding
- Chemical Sciences, Geo-sciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy [DE-FG02-07ER15893]
- National Science Foundation GRFP
- Alexander von Humboldt Foundation
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In this work, we prepared, isolated, and structurally characterized a zirconium complex having a terminally bound imide motif, (PN)(2)Zr ENH (PN- = (N-(2-Pr-i(2)-4-methylpheny1)-2,4,6-trimethylanilide)), along with the zirconium nitride complex {(PN)(2)Zr N[mu(2)-Li(THF)]}(2). (PN)(2)Zr NH was prepared by reduction of trans-(PN)(2)Zr(N-3)(2) with KC8. Isotopic labeling and spectroscopic studies were conducted using the respective N-15 enriched isotopologues, whereas solid-state structural studies confirmed some of the shortest Zr N distances known to date (Zr NH, 1.830(3) angstrom; Zr N-, 1.822(2) angstrom). It was found that the nitride in {(PN)(2)Zr N[mu(2)-Li(THF)]}(2) is super basic and in the range of -36 to -43 pK(b) units. Computational studies have been applied to probe the bonding and structure for this new class of zirconium-nitrogen multiple bonds.
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