AbstractAn improved synthesis of 4,4‐bis(hydroxymethyl)‐1,2‐diselenolane and the complexation properties of the corresponding diselenolato dianion to group‐10 metals are reported. We describe an efficient and straightforward procedure that bypasses the isolation of the malodorous and air‐sensitive diselenol and starts with the diselenide and an appropriate group‐10 metal complex bearing phosphane and chlorido ligands. A series of complexes with various mono‐ and bidentate phosphanes is prepared and characterised by multinuclear NMR spectroscopy, mass spectrometry, and elemental analysis. Furthermore, the structure of most complexes is studied by single‐crystal X‐ray diffraction to establish their supramolecular arrangement in the solid state. Consequently, several group‐10 metal complexes with P–M–P angles (bite angles) in the range from 71–108° are investigated. The use of the sterically demanding bridging phosphane 4,5‐bis(diphenylphosphanyl)‐9,9‐dimethylxanthene, which exhibits a large bite angle yields a mixture of a di‐ and trinuclear complex. While the platinum‐containing complexes are proven to be rather stable, the palladium and nickel analogues tend to decompose. Especially, the nickel complexes were found to be sensitive against oxidation. This circumstance leads to the formation of the so far unknown 1,8‐bis(diphenylphosphanyl)naphthalene monooxide, the formation and structure of which could be confirmed from NMR spectroscopic data and single‐crystal X‐ray diffraction.