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trans‐[PtCl2(PHtBu2)2] (1) was thoroughly characterised by 1H, 31P{1H} and 195Pt{1H} NMR spectroscopy. Two rotational conformers were found to be stable in solution at room temperature. Force field calculations confirmed that these two conformers are very similar in energy. They co‐crystallise in the tetragonal space group P4bar as revealed by X‐ray diffraction studies. The dynamics of trans‐[PtCl2(PHtBu2)2] is here reported together with spectroscopic evidence of a phosphido‐bridged reduction product.

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