Caught in the Act of Substitution: Interadsorbate Effects on an Atomically Precise Fe/Co/Se Nanocluster.

Directing groups guide substitution patterns in organic synthetic schemes, but little is known about pathways to control reactivity patterns, such as regioselectivity, in complex inorganic systems such as bioinorganic cofactors or extended surfaces. Interadsorbate effects are known to encode surface reactivity patterns in inorganic materials, modulating the location and binding strength of ligands. However, owing to limited experimental resolution into complex inorganic structures, there is little opportunity to resolve these effects on the atomic scale.

Metal/Support Interactions Regulate Substrate Binding in Fe/Co/Se Cluster Catalysts.

Here, we investigate the stereoelectronic requirements of a family of Fe/CoSe molecular clusters to achieve a Goldilocks regime of substrate affinity for the catalytic coupling of tosyl azide and -butyl isocyanide. The reactivity of a catalytically competent iron-nitrenoid intermediate, observed , is explored toward nitrene transfer and hydrogen-atom abstraction. The dual role of isocyanide, which, on the one hand, prevents catalyst degradation but, in large amounts, slows down reactivity, is exposed.

P-Alkynyl functionalized benzazaphospholes as transmetalating agents.

Exposure of 10π-electron benzazaphosphole 1 to HCl, followed by nucleophilic substitution with the Grignard reagent BrMgCCPh afforded alkynyl functionalized 3 featuring an exocyclic -C[triple bond, length as m-dash]C-Ph group with an elongated P-C bond (1.7932(19) Å). Stoichiometric experiments revealed that treatment of trans-Pd(PEt3)2(Ar)(i) (Ar = p-Me (C) or p-F (D)) with 3 generated trans-Pd(PEt3)2(Ar)(CCPh) (Ar = p-Me (E) or p-F (F)), 5, which is the result of ligand exchange between P-I byproduct 4 and C/D, and the reductively eliminated product (Ar-C[triple bond, length as m-dash]C-Ph).