The 17e(-) monoradical [Mn(CO)5 ] is widely recognized as an unstable organometallic transient and is known to dimerize rapidly with the formation of a MnMn single bond. As a result of this instability, isolable analogues of [Mn(CO)5 ] have remained elusive. Herein, we show that two sterically encumbering isocyanide ligands can destabilize the MnMn bond leading to the formation of the isolable, manganese(0) monoradical [Mn(CO)3 (CNAr(Dipp2) )2 ] (Ar(Dipp2) =2,6-(2,6-(iPr)2 C6 H3 )2 C6 H3 ). The persistence of [Mn(CO)3 (CNAr(Dipp2) )2 ] has allowed for new insights into nitrosoarene spin-trapping studies of [Mn(CO)5 ].

The preparation of 3D and 2D Cu(I) coordination networks using ditopic m-terphenyl isocyanides is described. The incorporation of sterically encumbering substituents enables the controlled, solid-state preparation of Cu(I) tris-isocyanide nodes with a labile solvent ligand in a manner mirroring solution-phase chemistry of monomeric complexes. The protection afforded by the m-terphenyl groups is also shown to engender significant stability towards heat as well as acidic or basic conditions, resulting in robust single-metal-node networks that can transition from 3D to 2D extended structures.

The development of catalysts capable of fast, robust C-H bond amination under mild conditions is an unrealized goal despite substantial progress in the field of C-H activation in recent years. A Mn-based metal-organic framework (CPF-5) is described that promotes the direct amination of C-H bonds with exceptional activity. CPF-5 is capable of functionalizing C-H bonds in an intermolecular fashion with unrivaled catalytic stability producing >10 turnovers.

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A permanently porous, three-dimensional metal-organic material formed from zero-valent metal nodes is presented. Combination of ditopic m-terphenyl diisocyanide, [CNAr], and the d Ni(0) precursor Ni(COD), produces a porous metal-organic material featuring tetrahedral [Ni(CNAr)] structural sites. X-ray absorption spectroscopy provides firm evidence for the presence of Ni(0) centers, whereas gas-sorption and thermogravimetric analysis reveal the characteristics of a robust network with a microdomain N-adsorption profile.