Compared to other zerovalent homoleptic trimethylphosphine complexes, W(PMe3)6 was less straightforward to synthesize and isolate.

Previous attempts to prepare W(PMe3)6 by co-condensation (a modification of metal vapor synthesis) of tungsten with PMe3 and reduction of WCl6 with alkali metal reducing agents only formed the cyclometalated W(PMe3)4(η2-CH2PMe2)H.[1] W(PMe3)6 was first isolated in 1990 by Parkin and Rabinovich.

Parkin and Rabinovich modified this preparation by simply stirring a mixture of WCl6 and Na(K) alloy in PMe3 at room temperature for 10 days.

[3] These complexes have been shown to be capable of activating C-H and other otherwise unreactive σ-bonds via oxidative addition, often forming cyclometalated products.

Interaction of the appropriate dichlorophosphane with W(PMe3)6 leads to dechlorination and formation of symmetrical and unsymmetrical diphosphenes.The resultant phosphorus-tungsten species can also catalyze the exchange of diphosphene end-groups.