Modulation of H+/H- exchange in iridium-hydride 2-hydroxypyridine complexes by remote Lewis acids.

A series of iridium hydride complexes featuring dihydrogen bonding are presented and shown to undergo rapid H+/H- exchange (1240 s-1 at 25 °C). We demonstrate that the H+/H- exchange rate can be modified by post-synthetic modification at a remote site using BH3, Zn(C6F5)2, and [Me3O][BF4]. This route provides a complementary strategy to traditional methods that rely on pre-metalation modifications to a metal's primary sphere.

Phenylamino derivatives of tris(2-pyridylmethyl)amine: hydrogen-bonded peroxodicopper complexes.

A series of copper complexes bearing new 6-substituted tris(2-pyridylmethyl)amine ligands (LR) appended with NH(p-R-C6H4) groups (R = H, CF3, OMe) were prepared. These ligands are electronically tunable (ΔE1/2 = 160 mV) and CuI(LR)+ complexes react with oxygen to form hydrogen bonded (trans-1,2-peroxo)dicopper species.