Despite the long-standing history and remarkable stability of low-valent mercury compounds, their use in molecular reduction chemistry has remained largely unexplored. In particular, the ability of me...

Late transition metal imido complexes in more than two oxidation states remain rare, owing to the intrinsic instability of metals in uncommon oxidation states, which typically exhibit strong reducing ...

In this communication, we revisit one of E. O. Fischer’s seminal discoveries to solve a textbook question: is the iron(0) complex [Fe(C6Me6)2] an 18-valence-electron complex with a ‘ring-slip’ (η6,η4)...

Hydrogen activation by stable carbenes is rare and typically proceeds through π-face, non-least-motion pathways. Now, a neutral σ0π2 carbene has been synthesized and shown to cleave H2 at room tempera...

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...

Since the isomerization of C–C multiple bonds is a powerful strategy in organic synthesis, in this study we have investigated the isomerization upon metalation of 1-phenylpropyne with alkyllithium bas...

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...

PhD Project - Combined Synthetic and Computational Understanding of New Heterobimetallic Dimetallocenes at The University of Manchester, listed on FindAPhD.com

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...

Could the discovery of a catalyst in which aluminium shifts easily between oxidation states be the beginning of the end for costly transition-metal catalysts?

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...

Carbon monoxide (CO) is one of the simplest and most fundamental molecules that has fascinated chemists for decades. Early-on, chemists have recognized and exploited its favorable properties as a key ...

We describe the reaction between the linear iron(I/II) silylamides [FeL2]0,– (L = N{Dipp}SiMe3) and aryl azides N3R with different steric demand (R = Ph, 2-Me-C6H4 (Tol), 2,4-Me2-C6H3 (Xyl), 2,6-iPr2-...

PhD Project - PhD Studentship in C–H Functionalisation Using Polymetallic Complexes at Imperial College London, listed on FindAPhD.com

PhD Project - Sustainable Catalysis with Sb and Bi Pincer Complexes at The University of Manchester, listed on FindAPhD.com

Nature Synthesis - Dynamic Al–Cd frameworks

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 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).

A series of cationic nido-clusters [E(η4-IDP)]+/2+ was prepared from the imidazolium-substituted diphosphate-diide (IPr)2C2P2 (IDP), including [1]+ (E = Ga) and [2b,c]2+ (E = Sn, Pb). As analogues of ...

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The nickel-catalyzed Kumada–Tamao–Corriu cross-coupling reaction is widely used to form C–C bonds and receives continued interest due to the unique ability of nickel to activate challenging organic electrophiles containing C–F and C–O bonds. Recent studies on the nickel-catalyzed cross-coupling of Ar–F and Ar–OMe electrophiles with organolithium nucleophiles have unveiled the key involvement of highly reactive anionic nickelates, in which Li and Ni cooperatively promote the activation of these substrates. However, the possible formation of related heterobimetallic intermediates when employing organomagnesium nucleophiles as cross-coupling partners still remains widely underexplored. Filling this gap in the knowledge, we use air-stable Ni-tris(olefin), Ni(4-Me-stb)3 (where stb = stilbene), as a Ni(0) precursor to systematically investigate its reactivity toward several organomagnesium and organolithium reagents, which has allowed for the structural and spectroscopic characterization of a new family of nickelate complexes. Their possible implications and the influence of their constitution and speciation on the outcome of Kumada–Tamao–Corriu cross-couplings are also investigated through a series of stoichiometric and catalytic reactions, which have uncovered a dramatic solvent effect, hinting at the formation of contacted ion pair species as key to maximizing Mg (or Li)/Ni(0) cooperativity.

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...

In this work, we disclose the synthesis and characterization of non-acid/base-stabilized anionic oxoboranes [MesTer2BO][K(L)] (MesTer = –C6H3-2,6-(2,4,6-Me3-C6H2)2, L = [2.2.2]-cryptand or 18-crown-6)...

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.