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 ...

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.