Varying the Lewis Base Coordination of the Y2N2Core in the reduced dinitrogen complexes {[(Me3Si)2N]2(L)Y}2(μ-η2:η2-N2) (L = benzonitrile, pyridines, triphenylphosphine oxide, and trimethylamine N-oxide)

Corbey, J. F., Farnaby, J. H. , Bates, J. E., Ziller, J. W., Furche, F. and Evans, W. J. (2012) Varying the Lewis Base Coordination of the Y2N2Core in the reduced dinitrogen complexes {[(Me3Si)2N]2(L)Y}2(μ-η2:η2-N2) (L = benzonitrile, pyridines, triphenylphosphine oxide, and trimethylamine N-oxide). Inorganic Chemistry, 51(14), pp. 7867-7874. (doi: 10.1021/ic300934g) (PMID:22757962)

Abstract

The effect of the neutral donor ligand, L, on the Ln2N2 core in the (N═N)2– complexes, [A2(L)Ln]2(μ-η2:η2-N2) (Ln = Sc, Y, lanthanide; A = monoanion; L = neutral ligand), is unknown since all of the crystallographically characterized examples were obtained with L = tetrahydrofuran (THF). To explore variation in L, displacement reactions between {[(Me3Si)2N]2(THF)Y}2(μ-η2:η2-N2), 1, and benzonitrile, pyridine (py), 4-dimethylaminopyridine (DMAP), triphenylphosphine oxide, and trimethylamine N-oxide were investigated. THF is displaced by all of these ligands to form {[(Me3Si)2N]2(L)Y}2(μ-η2:η2-N2) complexes (L = PhCN, 2; py, 3; DMAP, 4; Ph3PO, 5; Me3NO, 6) that were fully characterized by analytical, spectroscopic, density functional theory, and X-ray crystallographic methods. The crystal structures of the Y2N2 cores in 2–5 are similar to that in 1 with N–N bond distances between 1.255(3) Å and 1.274(3) Å, but X-ray analysis of the N–N distance in 6 shows it to be shorter: 1.198(3) Å.

• Item Type: Articles
• Additional Information: The authors thank the U.S. National Science Foundation [CHE- 1010002 (W.J.E.) and CHE-0840513 (F.F.)] for support of this research.
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Farnaby, Dr Joy
• Authors: Corbey, J. F., Farnaby, J. H., Bates, J. E., Ziller, J. W., Furche, F., 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: 03 July 2012