Two-Site O-H Addition to an Iridium Complex Featuring a Nonspectator Tricoordinate Phosphorus Ligand.

The synthesis and reactivity of an ambiphilic iridium complex IrCl(PPh)() (; = P(N(-N(2-pyridyl)CH))) featuring a chelating nontrigonal phosphorus triamide ligand is reported. The tandem Lewis basic Ir and Lewis acidic P of achieve a two-site oxidative addition of phenol giving the iridaphenoxyphosphorane species IrHCl(PPh)() (). In contrast, reactions of with benzenethiol and benzeneselenol do not engage and instead proceed via metal-centered oxidative addition of the chalcogen-hydrogen bond.

A closed-shell monomeric rhenium(1-) anion provided by m-terphenyl isocyanide ligation.

The mixed isocyanide/carbonyl complexes cis- and trans-[Re(CO)3Br(CNArDipp2)2] (ArDipp2 = 2,6-(2,6-(i-Pr)2C6H3)2C6H3) can be synthesized from reactions of [Re(CO)5Br] and CNArDipp2 depending on the conditions applied. Reduction of the neutral Re(i) species gives the monoanionic complex [Re(CO)3(CNArDipp2)2]- or the neutral [Re(CO)3(CNArDipp2)2], which contain rhenium in the formal oxidation states "-1" and "0", respectively.

Terminal coordination of diatomic boron monofluoride to iron.

Boron monofluoride (BF) is a diatomic molecule with 10 valence electrons, isoelectronic to carbon monoxide (CO). Unlike CO, which is a stable molecule at room temperature and readily serves as both a bridging and terminal ligand to transition metals, BF is unstable below 1800°C in the gas phase, and its coordination chemistry is substantially limited. Here, we report the isolation of the iron complex Fe(BF)(CO)(CNAr) [Ar, 2,6-(2,4,6-(Pr)CH]CH; -Pr, -propyl], featuring a terminal BF ligand.

Controlled Expansion of a Strong-Field Iron Nitride Cluster: Multi-Site Ligand Substitution as a Strategy for Activating Interstitial Nitride Nucleophilicity.

Multimetallic clusters have long been investigated as molecular surrogates for reactive sites on metal surfaces. In the case of the μ -nitrido cluster [Fe (μ -N)(CO) ] , this analogy is limited owing to the electron-withdrawing effect of carbonyl ligands on the iron nitride core. Described here is the synthesis and reactivity of [Fe (μ -N)(CO) (CNAr ) ] , an electron-rich analogue of [Fe (μ -N)(CO) ] , where the interstitial nitride displays significant nucleophilicity.