The simplistic methylbismuth dication has been captured only by the aid of monodentate tetrahydrofuran (thf) ligands, [BiMe(thf)5]2+. The hexacoordinate species shows a very unusual pentagonal pyrami...

We report a high-yielding synthesis of a novel diazadiphospholenium cation featuring a sterically exposed, reactive P [[double bond, length half m-dash]] P bond. It displays aromatic properties and gr...

We describe the synthesis and isolation of a phosphinidene telluride. This species acts as a versatile phosphinidene transfer reagent accompanied by the extrusion of elemental tellurium.

[K@crypt-222][TeCN] was synthesized from KCN, Te, and crypt-222 in acetone. We discuss fundamental properties of [TeCN]−: Single crystal X-ray diffraction, nuclear magnetic resonance (13C, 15N, 125Te...

The perfluoropinacol borate-based anion [B(O2C2(CF3)4)2]−, [FPB]–, is developed as a weakly coordinating anion for single-crystal to single-crystal organometallic solid/gas reactivity, resulting in the isolation and characterization (including periodic DFT and IGMH analysis) of the σ-alkane complex [Rh(Cy2PCH2CH2PCy2)(exo-η2η2-norbornane)][FPB]. The synthetically useful solvent-free Na+ salt, Na[FPB], and oxonium acid [H(OEt2)2][FPB] are also reported.

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 ...

We have developed C6F5BH2·SMe2 as a unique, metal-free precatalyst for alkene hydroboration. It combines high reactivity and excellent regio- and chemoselectivity. Mechanistic studies reveal that the ...

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.

Whilst bis(trimethylsilyl)amide has been used extensively as a ligand across the periodic table, the chemistry of its heavier group 15 congeners is relatively underdeveloped. However, bis(trimethylsil...

By linking N-heterocyclic olefins with a P-substituted indenyl heterocycle, it was possible to synthesize a very exciting new heterocyclic substance class that is both zwitterionic and diradical. 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...