Abstract
The structure of WCl2(PMe3)4 has been determined in order to allow for a comparison with its molybdenum analogue. The complexes are isomorphous, and exhibit trans-pseudooctahedral coordination, with crystallographically imposed $$\overline{4}2m$$ (D2d) symmetry. A significant distortion occurs involving the PMe3 ligands, through which one opposing pair tilts upward toward one axial chloride ligand, while the other pair tilts in an opposite manner, by 9.33°. The complex crystallizes in the tetragonal space group $$I\overline{4}2m$$ , with a = b = 9.4987(4) A, c = 12.1058(5) A, V = 1092.25(8) A3, D calc = 1.700 at 150(1) K. For a better comparison, the structure of the molybdenum complex was redetermined, at a low temperature. Its space group is also $$I\overline{4}2m$$ with a = b = 9.5193(3) A, c = 12.1083(5) A, V = 1097.22 A3, D calc = 1.426 at 150(1) K. In accord with the larger cell volume, the molybdenum complex possesses slightly longer M–Cl and M–P bonds.
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