Syntheses and characterization of the W(II) and W(III) N2 complexes, [WCl2(PMe3)3]2N2 and [WCl3(PMe3)2]2N2

Refluxing WCl4(PMe3)3 under a nitrogen atmosphere in the presence of two equivalents of sodium amalgam leads to a reduction to the W(II) complex [cis,mer-WCl2(PMe3)3]2N2 (1), which can be converted to [mer,trans-WCl3(PMe3)2]2N2 (2) via appropriate oxidation/chlorination. Structural data have been obtained for both complexes, and demonstrate significantly increased steric crowding in 1 due to PMe3/PMe3 interactions. The N–N bond distances in the two compounds are similar, at 1.279(4) and 1.243(18) Å, respectively.