The compoundtrans-[MoCl2(PMe2Ph)4] has been prepared by the reduction of MoCl5 (by Mg) or of [MoCl3(PMe2Ph)3] (by LiBun) in the presence of PMe2Ph in tetrahydrofuran (THF). It has μeff=2.84 B.M. and crystallises in space group P1 witha=11.591(3),b=12.931(3),c=12.703(3) A, α= 95.28(2), β=105.97(2), γ=103.54(2)°. Refinement of the structure gave R=0.036. The Mo-Cl and Mo-P distances average 2.443(6) and 2.534(8) A, respectively. Low-valent phosphine complexes of the Group VI metals continue to attract much attention because of their involvement in studies of the catalytic activation of dinitrogen(1), dihydrogen(2, 3), alkenes and alkynes(4). As a by-product during our studies of dinitrogen(1) and hydride(2) complexes of molybdenum and tungsten, we obtainedtrans-[MoCl2- (PMe2Ph)4] as yellow, paramagnetic crystals (μeff= 2.84 B.M.). We first obtained the compound during the attempted synthesis ofcis-[Mo(N2)2(PMe2Ph)4] by reduction of MoCl5 with Mg in the presence of PMe2Ph (see Experimental). Upon identification of the compound we found that it could be readily synthesised by treatment of [MoCl3(PMe2Ph)3](5) with LiBun in THF in the presence of PMe2Ph (experimental). The complex was shown to have thetrans structure by x-ray analysis (Figure). Analogues oftrans-[MoCl2(PMe2Ph)4] have been prepared, namely [CrCl2(Me2PCH2CH2PMe2)2](6),trans- [MoCl2(PMe3)4](7), [WCl2(PMe2Ph)4](8) and [WCl2(PMe3)4](4), of which onlytrans-[MoCl2(PMe3)4] has been examined by X-rays(7). Its principal structural parametersi.e. d(Mo-Cl)= 2.420(6), d(Mo-P)av=2.496(3) A(6) are close to those found here fortrans-[MoCl2(PMe2Ph)4].