Complete inorganic sandwich complexes with group 15 element rings at a single metal center have remained elusive for more than 30 years. Herein, we report that the readily accessible Zintl ion E73– (E...

Sandwich compounds are foundational to organometallic chemistry, yet carbon-free analogs remain exceptionally rare. We report the all-phosphorus heteroleptic cobalt sandwich anion [(η5-P5)Co(η3-P3)]− ...

The reaction of [K(thf)0.33][Co(η4-cod)2] (E; cod = 1,5-cyclooctadiene) with 0.5 equiv of MgCl2 led to the isolation of the magnesium dicobalt complex Mg[Co(η4-cod)2]2 (1). Complex 1 forms a tight ionic complex in the solid state and in toluene solution due to electrostatic interactions between the Mg2+ cation and the [Co(η4-cod)2]− anions. The complex is a successful precatalyst for the hydrogenation of sterically challenging tri- and tetra-substituted alkenes, surpassing the catalytic capabilities of related alkali metal and β-diketiminate magnesium complexes.

Aryl and alkyl chlorides are inexpensive and readily accessible, making them ideal reagents for converting white phosphorus (P4) into primary phosphines RPH2. However, methods for achieving this…

Linear 3d-metal complexes with open-shell metal ions have fascinated coordination chemists for decades. Originally the focus lied on metal(II) species, yet the synthetic possibilities to acquire their...

This minireview discusses the facilitation of E─C bond homolysis of main group compounds with visible light by the coordination of redox non-innocent ligands. Important conceptual coherencies, potent....

Photoredox chemistry has seen a dramatic rise in popularity in recent years, but mechanistic understanding has persistently lagged behind reaction development itself. This is particularly true for the...

We report the [2+2]-cyclization reaction of a phosphaalumene with its lighter analog, an iminoborane, to give a species with a four-membered BNAlP-heterocycle with alternating Lewis basic and acidic c...

Heavier transition metal carbyne analogs hold significant potential for cooperative activation of small molecules. However, complexes containing more than one heavier tetrylidyne ligand RE (E = Si, Ge...

Nitrenes (R–N) have been subject to a large body of experimental and theoretical studies. The fundamental reactivity of this important class of transient intermediates has been attributed to their electronic structures, particularly the accessibility of triplet vs singlet states. In contrast, electronic structure trends along the heavier pnictinidene analogues (R–Pn; Pn = P–Bi) are much less systematically explored. We here report the synthesis of a series of metallodipnictenes, {M–Pn═Pn–M} (M = PdII, PtII; Pn = P, As, Sb, Bi) and the characterization of the transient metallopnictinidene intermediates, {M–Pn} for Pn = P, As, Sb. Structural, spectroscopic, and computational analysis revealed spin triplet ground states for the metallopnictinidenes with characteristic electronic structure trends along the series. In comparison to the nitrene, the heavier pnictinidenes exhibit lower-lying ground state SOMOs and singlet excited states, thus suggesting increased electrophilic reactivity. Furthermore, the splitting of the triplet magnetic microstates is beyond the phosphinidenes {M–P} dominated by heavy pnictogen atom induced spin–orbit coupling.

Terminal metal–phosphorus (M–P) complexes are of significant contemporary interest as potential platforms for P-atom transfer (PAT) chemistry. Decarbonylation of metal–phosphaethynolate (M–PCO) comple...