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Updated: May 25, 2025

Preparation of N-2-alkoxyvinylsulfonamides from N-tosyl-1,2,3-triazoles and Subsequent Conversion to Substituted Phthalans and Phenethylamines
Published on: January 3, 2018
Promoting π-Facial Interactions in Phenyl-Substituted 1,8-Bis(silylamido)naphthalene Alkaline Earth Complexes
Matthew D Haynes1, Clement G Collins Rice1, Louis J Morris1
1Chemistry Research Laboratory, Department of Chemistry, University of Oxford, 12 Mansfield Road, OX1 3TA Oxford, U.K.
Abstract:
Bimetallic 1,8-bis(silylamido)naphthalene alkaline earth complexes [(R L)Ae]2 ([R L]2- = [1,8-{(R3Si)N}2C10H6)]2-, where R3 = Ph2Me, Ae = Ca (1), Sr (2), and Ba (3); R3 = Ph3, Ae = Ca (4), Sr (5), and Ba (6) were prepared via protonolysis reactions of the phenyl-substituted proligands Ph LH2 and PhLH2 with [AeN″2]2 (N″ = [N(SiMe3)2]-) in benzene. X-ray crystallographic analysis showed that 1, 2, and 4 crystallize as nitrogen-bridged dimers. Conversely, 5 and 6 display a naphthalene-bridged motif, while the structure of 3 is intermediate between the two distinct classes. NMR spectroscopic analysis of isolated samples of 1-6 in thf-d 8 confirmed their conversion into the monomeric thf-d 8 adducts [(R L)Ae(thf-d 8) ]; crystallographic verification of the structural motif was provided by the X-ray crystal structure of [(Ph L)Sr(thf)3] (7). The structural range of dimers 1-6 was influenced by the electron-withdrawing nature of the phenyl substituents of the ligand and the ability to form "soft" multihaptic π-facial interactions with the metal ions, which was preferential for the larger Sr2+ and Ba2+ cations as well as the relative strength of the metal-N bonds. This has been rationalized through complementary computational studies. This work provides insight into the structure and bonding preferences of heavy alkaline earth complexes with rigid bis(amido) ligands.
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