White phosphorus, generated in the legacy thermal process for phosphate rock upgrading, has long been the key industrial intermediate for the synthesis of phosphorus-containing chemicals, including herbicides, flame-retardants, catalyst ligands, battery electrolytes, pharmaceuticals, and detergents. In contrast, phosphate fertilizers are made on a much larger scale from phosphoric acid, obtained by treating phosphate rock with sulfuric acid. Dehydration of phosphoric acid using sodium chloride gives trimetaphosphate, and here we report that trichlorosilane, primarily used for the production of high-purity silicon, reduces trimetaphosphate to the previously unknown bis(trichlorosilyl)phosphide anion. This anion offers an entry point to value-added organophosphorus chemicals such as primary and secondary alkyl phosphines, and thus to organophosphinates, and can also be used to prepare phosphine gas and the hexafluorophosphate anion, all previously available only downstream from white phosphorus.

A synthesis of the 2‐phosphathioethynolate anion, PCS–, under ambient conditions is reported. The coordination chemistry of PCO–, PCS– and their nitrogen‐containing congeners is also explored. Photolysis of a solution of W(CO)6 in the presence of PCO– [or a simple ligand displacement reaction using W(CO)5(MeCN)] affords [W(CO)5(PCO)]– (1). The cyanate and thiocyanate analogues, [W(CO)5(NCO)]– (2) and [W(CO)5(NCS)]– (3), are also synthesised using a similar methodology, allowing for an in‐depth study of the bonding properties of this family of related ligands. Our studies reveal that, in the coordination sphere of tungsten(0), the PCO– anion preferentially binds through the phosphorus atom in a strongly bent fashion, while NCO– and NCS– coordinate linearly through the nitrogen atom. Reactions between PCS– and W(CO)5(MeCN) similarly afford [W(CO)5(PCS)]–; however, due to the ambidentate nature of the anion, a mixture of both the phosphorus‐ and sulfur‐bonded complexes (4a and 4b, respectively) is obtained. It was possible to establish that, as with PCO–, the PCS– ion also coordinates to the metal centre in a bent fashion.

Industrial and laboratory methods for incorporating phosphorus atoms into molecules within the framework of Green Chemistry are in their infancy. Current practice requires large inputs of energy, involves toxic intermediates, and generates substantial waste. Furthermore, a negligible fraction of phosphorus-containing waste is recycled which in turn contributes to negative environmental impacts, such as eutrophication. Methods that begin to address some of these drawbacks are reviewed, and some key opportunities to be realized by pursuing organophosphorus chemistry under the principles of Green Chemistry are highlighted. Methods used by nature, or in the chemistry of other elements such as silicon, are discussed as model processes for the future of phosphorus in chemical synthesis.

Acyl(chloro)phosphines RC(O)P(Cl)(t-Bu) have been prepared by formal insertion of tert-butyl phosphinidene (t-Bu–P) from t-BuPA (A = C14H10 or anthracene) into the C–Cl bond of acyl chlorides.

Fusion proteins play an essential role in the biosciences but suffer from several key limitations, including the requirement for N-to-C terminal ligation, incompatibility of constituent domains, incorrect folding, and loss of biological activity. This perspective focuses on chemical and enzymatic approaches for the post-translational generation of well-defined protein−protein conjugates, which overcome some of the limitations faced by traditional fusion techniques. Methods discussed range from chemical modification of nucleophilic canonical amino acid residues to incorporation of unnatural amino acid residues and a range of enzymatic methods, including sortase-mediated ligation. Through summarizing the progress in this rapidly growing field, the key successes and challenges associated with using chemical and enzymatic approaches are highlighted and areas requiring further development are discussed.