Despite recent proof-of-concept advances, aromatic carbon-to-nitrogen replacement reactions remain substrate specific and exhibit an overreliance on harsh oxidation methods that preclude their deploym...

Abstract. Bimetallic cooperative catalysis has overcome many of the established mechanistic limitations of monometallic reactivity in activating and transf

Molecules showing magnetic memory effects at high temperatures could be used in high-density data storage devices but often exhibit fast magnetic relaxation at lower temperatures. Here the authors rep...

The ring-opening polymerization (ROP) of δ-lactones derived from the telomerization of CO2 and butadiene offers a platform to valorize cheap and abundant waste products into commercially competitive p...

The direct functionalization of white phosphorus (P4) is gaining attention as an alternative to state-of-the-art multi-step processes. The hydrostannylation of P4 affords valuable monophosphorus compo...

The unique photophysical properties of heavy T-shaped Sb and Bi trisamides are reported. A ligand-to-pnictogen charge-transfer excitation from a redox-active NNN pincer to a vacant pnictogen p-orbita...

Systematic pnictogen variation (P, As, Sb, Bi) in PnMes3–B(C6F5)3 Frustrated Lewis Pairs (FLPs) reveals how both the energy and intensity of charge–transfer excitation can be tuned. Increasing pnicto...

Titanocene phosphinidenes react with terminal alkynes in formal [2 + 2] cycloadditions to give unsaturated [C2PTi] metallcycles. Diphosphene complexes in combination with aryl-substituted alkynes rea...

We report the synthesis and comprehensive characterisation of a square-planar Si(+IV) hydride supported by an unsymmetric, trianionic and dearomatised N,N,N-pincer ligand. This system enables element...

Molecular complexes of iron in the rare +1 oxidation state have been shown to be efficient catalysts for industrially relevant chemical transformations, typically associated with the increasingly unsu...

Low-valent aluminum chemistry continues to expand the boundaries of main-group reactivity, yet the selective generation and transfer of Al(II) fragments remain underexplored. Controlled Al(II) transfe...

Im Jahr 2025 waren aller guten Dinge der Hauptgruppenchemie drei: ein dreifach geladenes Triborattrianion, ein Molekül mit linearer Al3-Einheit, das dritte Erdalkalimetall, das Stickstoff bindet, ein ...

We report the transition-metal-like reactivity of a geometrically constrained, ambiphilic bismuth(III) trisamide. Planarization of the Bi(III) center unlocks Bi–C bond formation when reacted with mild...

Low-valent cadmium compounds have remained largely unexplored as electron reservoirs, with no precedent for their use in reduction or bond activation chemistry. Here, we address this gap by integratin...

The β-diketiminato calcium hydride, [(BDI)CaH]2 (BDI = HC{(Me)CNDipp}2, where Dipp = 2,6-i-Pr2C6H3), reacts with [Zn{N(SiMe3)2}2] and [Zn(TMP)2] (TMP = 2,2,6,6-tetramethylpiperidide) to provide labile...

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 trans...

The reactivity of the kinetically stabilized stannylene (MesTer)2Sn (1) (MesTer = –C6H3-2,6-(2,4,6-Me3-C6H2)2) toward N2O is revisited, yielding the terminal tin(IV) hydroxide 2 via formal intramolecular C(sp3)–H activation of a putative terminal stannanone intermediate. By switching to Eind ligation (Eind = 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl) at the tin center, the synthesis and characterization of the crystalline lithium salt (Eind)Li(THF)2 (3) is reported, serving as a straightforward precursor for the clean generation of the corresponding stannylene (Eind)2Sn (4). Compound 4 can be further cleanly converted into the heteroleptic Eind/halide stannylene (Eind)SnCl (6). Both 4 and 6 serve as suitable precursors for the synthesis of the heteroleptic s-hydrindacene-/amido-substituted stannylene (Eind)Sn{N(SiMe3)2} (5).

Phosphaalkkenes are an underrepresented class of phosphorus-based ligands that hold great potential for the stabilisation of low-valent transition metal and main group fragments. We present the synthe...

The development of efficient, direct strategies for the transformation of white phosphorus (P4) into useful monophosphorus compounds, as alternatives to the current wasteful and hazardous indirect pro...

A major thrust of research in modern main group chemistry is the use of multidentate ligands to perturb geometries at p-block elements such that they deviate substantially from valence shell electron-...

The analytical techniques revealing the true identity of what you spread on your bread

Molecular chemistry of aluminum most commonly involves AlIII ions due to their noble gas electronic configurations. In contrast, the chemistry of AlII ions is underexplored and may contain undiscovere...

New aza-diphosphinanes have been prepared and a model has been developed to explain their cis/trans isomerization. Two-fold oxidation leads to new aza-diphosphazenanes as robust inorganic connectors ...

Cyclic anhydride and epoxide ring-opening copolymerization is a versatile and controlled route to make polyesters, gaining attention in different application sectors but so far the chemical recycling...

The reactivity of an unsupported phosphinidene oxide, BnArNP═O (Bn = benzyl; Ar = bulky aryl group), as the electrophilic partner in Wittig reactions with ylides is described. Reactions with methylene-triphenylphosphorane (H2C═PPh3) and ethylidene-triphenyl-phosphorane (HMeC═PPh3), proceed as expected, giving rise to the phosphaalkene metathesis products and triphenylphosphine oxide. This reaction can be extended to other ylides such as N-(triphenylphosphoranylidene)methanamine (MeN═PPh3), to afford an aminoiminophosphane BnArNP═NMe. In these reactions the phosphinidene oxide plays the role of an electrophile, which would typically be the remit of an organic carbonyl in classical Wittig reactions. Further mechanistic insight into such transformations can be gained by altering the nature of the phosphorus-ylide. Upon reacting BnArNP═O with H2C═PMe3 (which possesses a smaller, more Lewis basic, phosphine) an alternative product is formed. This transformation supports the formation of a betaine intermediate that subsequently undergoes hydrogen-migration to afford an oxidized phosphorus(V) compound related to phosphorus acid.

The dinuclear title compound [(Cp2Zr)2(µ-Me)(µ-C2Ph)] 5 was prepared from a zirconocene alkynyl methyl complex and Rosenthal’s zirconocene source [Cp2Zr(py)(h2-Me3SiC2SiMe3)] in a formal comproportio....

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...

The ubiquity of N-heterocyclic carbenes (NHCs) in chemical research typically arises from their potent stabilizing capabilities and role as innocent spectators to stabilize otherwise non-bottleable co...

Cyanophosphides of the general form [RPCN]− can be viewed as cyanide adducts of phosphinidenes and are phosphorus species in the (+1)-oxidation state. We have recently reported on the stable cyanophosphide [DippTerPCN]K (DippTer = 2,6-Dipp2C6H3, Dipp = 2,6-iPrC6H3) and now investigate its reactions with ECln (E = Ge, n = 2; E = P, As, n = 3) in either salt metathesis or base-assisted dehydrohalogenation reactions. In the case of GeCl2, salt metathesis with [DippTerPCN]K afforded the dimer of a chlorogermylene [DippTerP(CN)GeCl]2. When only 0.5 equiv of GeCl2 was used, the diphosphanylgermylene [DippTerP(CN)]2Ge was generated in solution. With ECl3 (E = P, As), facile cyanophosphide transfer was achieved from DippTerP(H)CN in NEt3-assisted dehydrohalogenation, giving diphosphanes or arsaphosphanes of the type DippTerP(CN)ECl2 (E = P, As), respectively.

The homogeneous catalytic functionalization of methane is extremely challenging due to the relative nonpolarity and high C–H bond strength of this hydrocarbon. Here, using catalytic quantities (10 mol...