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Under solar light at room temperature, the tungsten pentacarbonyl complex of the P–S–P-linked biphosphole (6) undergoes a [2+2] intramolecular cycloaddition. Then, this [2+2] dimer (7) gives the original [4+4] dimer (8) via a Cope rearrangement. This sequence stands in sharp contrast with the behavior of the corresponding P–O–P-linked biphosphole (2) which undergoes a classical [4+2] cycloaddition.
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