Reactivity of Iridium Complexes of a Triphosphorus-Pincer Ligand Based on a Secondary Phosphine. Catalytic Alkane Dehydrogenation and the Origin of Extremely High Activity

The selective functionalization of alkanes and alkyl groups is a major goal of chemical catalysis. Toward this end, a bulky triphosphine with a central secondary phosphino group, bis(2 di-t-butyl-phosphinophenyl)phosphine (tBuPHPP), has been synthesized. When complexed to iridium it adopts a meridional (“pincer”) configuration. The secondary phosphino H atom can undergo migration to iridium to give an anionic phosphido-based-pincer (tBuPPP) complex. We describe novel metal-ligand cooperativity of the iridium-phosphido unit. Stoichiometric reactions of the (tBuPPP)Ir complexes reflect a distribution of steric bulk around the iridium center in which the coordination site trans to the phosphido group is quite crowded, one coordination site cis to the phosphido is even more crowded, while the remaining site is particularly open. The (tBuPPP)Ir precursors are the most active catalysts reported to date for dehydrogenation of n-alkanes, by about two orders of magnitude. The electronic properties of the iridium center are very similar to that of well-known analogous (RPCP)Ir catalysts. Accordingly, DFT calculations predict that (tBuPPP)Ir and (tBuPCP)Ir are, intrinsically, comparably active for alkane dehydrogenation. While dehydrogenation by (RPCP)Ir proceeds through an intermediate trans-(PCP)IrH2(alkene), (tBuPPP)Ir follows a pathway proceeding via cis-(PPP)IrH2(alkene), thereby circumventing unfavorable placement of the alkene at the bulky site trans to phosphorus. (tBuPPP)Ir and (tBuPCP)Ir, however, have analogous resting states: square planar (pincer)Ir(alkene). Alkene coordination at the crowded trans site is therefore unavoidable in the resting states. Thus the resting state of the (tBuPPP)Ir catalyst is destabilized by the unusual architecture of the ligand, and this is largely responsible for its unusually high catalytic activity.

The structural basis of bacterial manganese import

Metal ions are essential for all forms of life. In prokaryotes, ATP-binding cassette (ABC) permeases serve as the primary import pathway for many micronutrients including the first-row transition metal manganese. However, the structural features of ionic metal transporting ABC permeases have remained undefined. Here, we present the crystal structure of the manganese transporter PsaBC from Streptococcus pneumoniae in an open-inward conformation. The type II transporter has a tightly closed transmembrane channel due to “extracellular gating” residues that prevent water permeation or ion reflux. Below these residues, the channel contains a hitherto unreported metal coordination site, which is essential for manganese translocation. Mutagenesis of the extracellular gate perturbs manganese uptake, while coordination site mutagenesis abolishes import. These structural features are highly conserved in metal-specific ABC transporters and are represented throughout the kingdoms of life. Collectively, our results define the structure of PsaBC and reveal the features required for divalent cation transport.

H2O coordination in macropa complexes of f elements (Ac, La, Lu): feasibility of the 11th coordination site

The feasibility of an additional ligand coordination at the 11th coordination site of actinium, lanthanum, and lutetium ions in 10-fold coordinated macropa complexes has been studied by means of density functional theory calculations. The study covered the two main macropa conformers, Δ(δλδ)(δλδ) and Δ(λδλ)(λδλ), favoured by larger (Ac3+, La3+) and smaller (Lu3+) ions, respectively. At the molecular level, the coordination of H2O is the most favourable to the largest Ac3+ while only slightly less to La3+. Protonation of the picoline arms enhances the coordination by shifting the metal ion closer to the open site of the ligand. The choice of macropa conformer has only a slight influence on the strength and bonding properties of the H2O coordination. Aqueous solution environment decreases considerably the energy gain of H2O coordination at the 11th coordination site.

Photo-oligomerization by shifting the coordination site in a luminescent coordination polymer

The photo-oligomerization of a diolefinic ligand by shifting the coordination site in a ZnII-based CP has been designed.