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).

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 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.

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...

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.