Expanding yttrium Bis(trimethylsilylamide) chemistry through the reaction chemistry of (N2)2–, (N2)3–, and (NO)2–complexes

Farnaby, J. H. , Fang, M., Ziller, J. W. and Evans, W. J. (2012) Expanding yttrium Bis(trimethylsilylamide) chemistry through the reaction chemistry of (N2)2–, (N2)3–, and (NO)2–complexes. Inorganic Chemistry, 51(20), pp. 11168-11176. (doi: 10.1021/ic301778q) (PMID:23036077)

Abstract

The reaction chemistry of the side-on bound (N2)2–, (N2)3–, and (NO)2– complexes of the [(R2N)2Y]+ cation (R = SiMe3), namely, [(R2N)2(THF)Y]2(μ-η2:η2-N2), 1, [(R2N)2(THF)Y]2(μ-η2:η2-N2)K, 2, and [(R2N)2(THF)Y]2(μ-η2:η2-NO), 3, with oxidizing agents has been explored to search for other (E2)n−, (E = N, O), species that can be stabilized by this cation. This has led to the first examples for the [(R2N)2Y]+ cation of two fundamental classes of [(monoanion)2Ln]+ rare earth systems (Ln = Sc, Y, lanthanides), namely, oxide complexes and the tetraphenylborate salt. In addition, an unusually high yield reaction with dioxygen was found to give a peroxide complex that completes the (N2)2–, (NO)2–, (O2)2– series with 1 and 3. Specifically, the (μ-O)2– oxide-bridged bimetallic complex, [(R2N)2(THF)Y}2(μ-O), 4, is obtained as a byproduct from reactions of either the (N2)2– complex, 1, or the (N2)3– complex, 2, with NO, while the oxide formed from 2 with N2O is a polymeric species incorporating potassium, {[(R2N)2Y]2(μ-O)2K2(μ-C7H8)}n, 5. Reaction of 1 with 1 atm of O2 generates the (O2)2– bridging side-on peroxide [(R2N)2(THF)Y]2(μ-η2:η2-O2), 6. The O–O bond in 6 is cleaved by KC8 to provide an alternative synthetic route to 5. Attempts to oxidize the (NO)2– complex, 3, with AgBPh4 led to the isolation of the tetraphenylborate complex, [(R2N)2Y(THF)3][BPh4], 7, that was also synthesized from 1 and AgBPh4. Oxidation of the (N2)2– complex, 1, with the radical trap (2,2,6,6-tetramethylpiperidin-1-yl)oxyl, TEMPO, generates the (TEMPO)− anion complex, (R2N)2(THF)Y(η2-ONC5H6Me4), 8.

• Item Type: Articles
• Additional Information: The authors thank the U.S. National Science Foundation (CHE-1010002) for support of this research.
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Farnaby, Dr Joy
• Authors: Farnaby, J. H., Fang, M., Ziller, J. W., and Evans, W. J.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Inorganic Chemistry
• Publisher: American Chemical Society
• ISSN: 0020-1669
• ISSN (Online): 1520-510X
• Published Online: 04 October 2012