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A new synthesis for trithiophosphonates from primary phosphines, nBuLi (or nBu2Mg) and elemental sulfur is presented and its mechanism investigated; the lithium and magnesium salts of cyclohexyltrithiophosphonate have been fully characterised to reveal dimers in the solid state in which all three of the trithiophosphonate sulfurs are involved in metal bonding.
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