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Metathetical reactions between TMEDA·Li[(H)C(PPh2Se)2] and MCl2 (M = Hg, Sn, Te) in a 2 : 1 molar ratio afforded the homoleptic complexes, {M[(H)C(PPh2Se)2]2}, as intermediates which undergo a surprising selenium/hydrogen exchange at the carbon centre to yield the dianionic triseleno ligand in {Mn[(Se)C(PPh2Se)2]2} (n = 1, M = Sn, Te; n = 2, M = Hg).

Graphical abstract: Novel carbon-centred reactivity of [(H)C(PPh2Se)2]− in the formation of structurally diverse Sn(iv), Te(iv) and Hg(ii) complexes of the triseleno ligand [(Se)C(PPh2Se)2]2–

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