Synthesis of a "super bulky" guanidinate possessing an expandable coordination pocket.

Friedel-Crafts alkylation of 4-tert-butylaniline with 2 equiv of benzhydrol affords bulky 2,6-bis(diphenylmethyl)-4-tert-butylaniline (Ar*NH2) in good yield, which can be readily synthesized on a tens of grams scale. The reaction of 6 equiv of Ar*NH2 with triphosgene generates the symmetric urea (Ar*NH)2CO, which, upon dehydration with a P2O5/Al2O3 slurry in pyridine, produces the sterically encumbered carbodiimide (Ar*N)2C as an air-stable white solid. The treatment of (Ar*N)2C with LiN═C(t)Bu2 in tetrahydrofuran cleanly gives the monomeric lithium guanidinate Li[(Ar)*ketguan], free of coordinating solvent, in 85% yield. Protonation of Li[(Ar)*ketguan] with lutidinium chloride produces the guanidine (Ar)*ketguanH (MW = 1112.60 g/mol), which is easily derivatized to give the monomeric alkali metal complexes M[(Ar)*ketguan] (M = K, Cs) in 94% and 51% yield, respectively. The solid-state molecular structures of M[(Ar)*ketguan] (M = Li, K, Cs) show formally two-coordinate alkali metal cations encapsulated within a hydrophobic coordination pocket formed by the peripheral diphenylmethyl substituents of the guanidinate. Remarkably, percent buried volume analyses (% V(Bur)) of M[(Ar)*ketguan] [M = Li (94.8% V(Bur)), K (92.1% V(Bur)), Cs (81.7% V(Bur))] reveal a coordination cavity that adjusts to individually accommodate the variously sized metal ions despite the highly encumbering nature of the ligand. This demonstrates a flexible ligand framework that is able to stabilize low-coordinate metal centers within a "super bulky" coordination environment.

A five-coordinate Ni(I) complex supported by 1,4,7-triisopropyl-1,4,7-triazacyclononane.

An isolated Ni(II)-nitrosyl complex supported by the bulky tridentate 1,4,7-triisopropyl-1,4,7-triazacyclononane (iPr3TACN) ligand was obtained from the reaction of a Ni(II) dimethyl complex with NOPF6, suggesting the in situ formation of a Ni(I) species that reacts with the resulting NO product. Use of a π-acceptor ancillary isocyanide ligand led to the isolation and characterization of an uncommon 5-coordinate Ni(I) complex supported by the iPr3TACN ligand and tert-butylisocyanide.